Tunable Directional Color Transition Compositions and Methods of Making and Using the Same

ABSTRACT

Color change compositions that transition from a first to second color state upon application of an applied stimulus are provided. Also provided are substrates having the compositions on a surface thereof, as well as methods of making and using the compositions.

CROSS-REFERENCE To RELATED APPLICATIONS

The application is a continuation of U.S. patent application Ser. No.14/040,461 filed Sep. 27, 2013, now U.S. Pat. No. 9,217,736, which is acontinuation of U.S. patent application Ser. No. 12/643,887 filed Dec.21, 2009, now U.S. Pat. No. 8,569,208. Pursuant to 35 U.S.C. §119 (e),this application claims priority to the filing date of U.S. ProvisionalPatent Application Ser. No. 61/238,584 filed Aug. 31, 2009 and U.S.Provisional Patent Application Ser. No. 61/140,563 filed Dec. 23, 2008;the disclosures of which applications are herein incorporated byreference.

SUMMARY

The invention involves tunable phase controllable systems for generatingcolor development reversibly, irreversibly, form colorless to a coloredstate based on ascending temperature, from a colored state to acolorless state based on descending temperature, solvation, hydration,or other chemical and physical stimuli to a colored state to a colorlessstate during the stimuli. Color transitions can be with and withoutcolor change hysteresis, including abrupt or broad transition colorchange options, utilize micro-encapsulation processes or un-encapsulatedprocesses, and can find use in a wide range of applications. Naturalproduct food-grade color developers are described for both ascending anddescending color change compositions. Further enabled are combinatorialchemistries including leuco dye color formers and polydiacetylenic-basedcompounds that serve both as developers and possess their own intrinsiccolor change properties are described herein.

DETAILED DESCRIPTION

Before the present invention is described in greater detail, it is to beunderstood that this invention is not limited to particular embodimentsdescribed, as such may, of course, vary. It is also to be understoodthat the terminology used herein is for the purpose of describingparticular embodiments only, and is not intended to be limiting, sincethe scope of the present invention will be limited only by the appendedclaims.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range and any other stated or intervening value in thatstated range, is encompassed within the invention. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges and are also encompassed within the invention, subject toany specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the invention.

Certain ranges are presented herein with numerical values being precededby the term “about.” The term “about” is used herein to provide literalsupport for the exact number that it precedes, as well as a number thatis near to or approximately the number that the term precedes. Indetermining whether a number is near to or approximately a specificallyrecited number, the near or approximating unrecited number may be anumber which, in the context in which it is presented, provides thesubstantial equivalent of the specifically recited number.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are now described.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present invention is not entitled to antedate suchpublication by virtue of prior invention. Further, the dates ofpublication provided may be different from the actual publication dateswhich may need to be independently confirmed.

It is noted that, as used herein and in the appended claims, thesingular forms “a”, “an”, and “the” include plural referents unless thecontext clearly dictates otherwise. It is further noted that the claimsmay be drafted to exclude any optional element. As such, this statementis intended to serve as antecedent basis for use of such exclusiveterminology as “solely,” “only” and the like in connection with therecitation of claim elements, or use of a “negative” limitation.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentinvention. Any recited method can be carried out in the order of eventsrecited or in any other order which is logically possible.

Compositions of the invention find use in a variety of applications,including but not limited to early stage production, manufacturing, orsynthesis stages through to end-of-use indication where a product orgood being monitored using an indicator or composition has alreadyexpired and is no longer of any further utility or value.

The invention discloses tunable phase controllable systems forgenerating color development reversibly, irreversibly, from colorless toa colored state based on ascending temperature, from a colored state toa colorless state based on descending temperature, solvation, hydration,or other chemical and physical stimuli to a colored state to a colorlessstate during the stimuli. Color transitions can be with and withoutcolor change hysteresis, including abrupt or broad transition colorchange options, utilize micro-encapsulation processes or un-encapsulatedprocesses, and can find use in a wide range of applications. Naturalproduct food-grade color developers are described for both ascending anddescending color change compositions. Further enabled are combinatorialchemistries including leuco dye color formers and polydiacetylenic-basedcompounds that serve both as developers and possess their own intrinsiccolor change properties which may or may not be utilized in conjunctionwith the invention and are described herein.

Tunable temperature indicating compositions can find use for a widerange of temperature, sensing, indicating, measurement, marking,cold-chain-management, perishable composition monitoring, safety,sensitizing, industrial, food service, pharmaceutical, industrial,processing, food processing, consumer products, household products, toyproducts, publishing, advertising, promotional dental, security,pharmaceutical, food products, novel packaging, skin care and skinhealth, pressure monitoring, temperature monitoring, humiditymonitoring, time monitoring, environmental monitoring, inventorymonitoring, medical and other market and/or product applications and thelike.

Example Permutations of Tunable Color Change Options:

Example permutations of tunable color change options include, but arenot limited to: reversible color to colorless based on temperature,reversible colorless to color based on temperature, reversible color tocolorless based on hydration, reversible colorless to color based onhydration, reversible color to colorless based on solvation, reversiblecolorless to color based on solvation, irreversible colorless to colorbased on temperature, irreversible color to colorless based onsolvation, reversible non-hysteresis color change, reversible colorchange with hysteresis types, irreversible non-hysteresis color change,irreversible color change with hysteresis types, hard/abrupt transitiontypes using precise melting point compositions as solvents, a wide rangeof temperature transition types and ranges, single color changetransition types, multiple color change transition types, and the like.

Reversible color development systems rather than conventional colorextinction systems have been of interest. Herein we provide simplesystems for developing color at increasing temperatures where the colordevelopment process can be reversed during descending temperatures.

Simple addition of phase separation compounds that act as developers inthe fluid or liquid state can interact with corresponding colordevelopers to develop a color during an elevated temperature phase.During the cooling phase, the color developer phase separates and itsability to interact as a color developer is diminished or eliminatedsuch that the cooling process gives rise to a loss of color. Conversely,as the temperature is elevated again and a phases separated colordeveloper becomes molten, mobile and capable of interacting with thecolor developer, a color is generated. Importantly, the process isreversible. Of further importance, the process, temperature settings,color types, hysteresis, and complexity of color change can be tuned byvarying degrees depending upon the composition of matter in the colordevelopment system.

Systems described herein can be non-microencapsulated ormicro-encapsulated depending on the formulation and product applicationof interest. A wide range of micro-encapsulation processes can beutilized in conjunction with the invention described.

Aspects of the embodiments of the invention include a color former andcolor developer. A variety of different types of color formers may beemployed, where examples of different color formers (e.g., dyes) arelisted below and specific examples are reported in the experimentalsection below.

Combined color former, e.g., leuco dye, systems can now allow for newpreviously unobtainable color changes such as red to green or green tored whereby two leuco dyes mixed together include a color to colorlessdye and a colorless to colored dye system. The resulting combination ofcolor to colorless and colorless to color in different combinationspermits the possibility of heretofore not realized color overlap suchthat stationary colors do not interfere with the initial or final color.

Co-developer/solvent systems for reversible ascending temperaturedependent color development:

Co-developer/solvent color developer co-monomer including, but notlimited to glycerol monostearate derivatives, low acidic phaseassociating compounds, mild protonating phase associating compounds, andthe like. Importantly, single component systems that provide the benefitof being both a solvent for promoting temperature dependent phase changeas well as a color developer that works in conjunction with a colorformer has an advantage of facilitating developing color upon increasingtemperature.

Importantly, co-developer/solvent compounds can assist in controllingthe ability of a developer by its ability to anneal or un-annealdepending on phase transition to create or abandon a charge transfercomplex through phase dissociation and association processes.Importantly, often co-developer/solvent compounds will be esterifiedwith hydroxyl containing groups. Derivatives include, but are notlimited to:

-   2,3-dihydroxypropyl C5-   2,3-dihydroxypropyl C7-   2,3-dihydroxypropyl C8-   2,3-dihydroxypropyl C9-   2,3-dihydroxypropyl C10-   2,3-dihydroxypropyl C11-   2,3-dihydroxypropyl C12-   2,3-dihydroxypropyl C13-   2,3-dihydroxypropyl C14-   2,3-dihydroxypropyl C15-   2,3-dihydroxypropyl C16-   2,3-dihydroxypropyl C17-   2,3-dihydroxypropyl C18-   2,3-dihydroxypropyl C19-   2,3-dihydroxypropyl C20-   2,3-dihydroxypropyl C21-   2,3-dihydroxypropyl C22-   2,3-dihydroxypropyl C23-   2,3-dihydroxypropyl C24-   2,3-dihydroxypropyl C25-   2,3-dihydroxypropyl C26-   2,3-dihydroxypropyl C27-   2,3-dihydroxypropyl C28-   2,3-dihydroxypropyl C29-   2,3-dihydroxypropyl C30-   3,4-dihydroxybutyl C5-   3,4-dihydroxybutyl C6-   3,4-dihydroxybutyl C7-   3,4-dihydroxybutyl C8-   3,4-dihydroxybutyl C9-   3,4-dihydroxybutyl C11-   3,4-dihydroxybutyl C12-   3,4-dihydroxybutyl C13-   3,4-dihydroxybutyl C14-   3,4-dihydroxybutyl C15-   3,4-dihydroxybutyl C16-   3,4-dihydroxybutyl C17-   3,4-dihydroxybutyl C18-   3,4-dihydroxybutyl C19-   3,4-dihydroxybutyl C20-   3,4-dihydroxybutyl C21-   3,4-dihydroxybutyl C22-   3,4-dihydroxybutyl C23-   3,4-dihydroxybutyl C24-   3,4-dihydroxybutyl C25-   3,4-dihydroxybutyl C26-   3,4-dihydroxybutyl C27-   3,4-dihydroxybutyl C28-   3,4-dihydroxybutyl C29-   3,4-dihydroxybutyl C30

Solvent/developer color developer co-monomer diacetylenicpolydiacetylene polymers including, but not limited to derivatives belowof, low acidic phase associating compounds, mild protonating phaseassociating compounds, and the like.

Example Diacetylenic Compounds:

-   2,3-dihydroxypropyl-10,12-dodecadiynoate (2,3-DHP-10,12-C12)-   2,3-DHP-10,12-C13-   2,3-DHP-10,12-C14-   2,3-DHP-10,12-C15-   2,3-DHP-10,12-C16-   2,3-DHP-10,12-C17-   2,3-DHP-10,12-C18-   2,3-DHP-10,12-C19-   2,3-DHP-10,12-C20-   2,3-DHP-10,12-C21-   2,3-DHP-10,12-C22-   2,3-DHP-10,12-C23-   2,3-DHP-10,12-C24-   2,3-DHP-10,12-C25-   2,3-DHP-10,12-C26-   2,3-DHP-10,12-C27-   2,3-DHP-10,12-C28-   2,3-DHP-10,12-C29-   2,3-DHP-10,12-C30

Hydrocarbon based solvents including, but not limited to:

-   n-Decane-   n-Decene-   n-Dodecane-   n-Dodecrne-   n-Tetradecane-   n-Tetradecene-   n-Hexadecane-   n-Hexadecene-   n-Octadecane-   n-Octadecene-   n-Eicosane-   n-Eicosene-   Paraffin Blend

Ester compounds can include, but are not limited to n-pentadecylacetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate,n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecylcaprylate, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptylcaprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate,n-pentadecyl caprate, n-pentyl laurate, n-heptyl laurate, n-nonyllaurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate,n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-undecylmyristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentylpalmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate,n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate,n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonylicosanoate, n-undecyl icosanoate, n-tridecyl icosanoate, n-pentadecylicosanoate, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate,and n-pentadecyl behenate. It is desirable for the esterifying group tobe hydroxylated in the event that the melting point medium is to be usedas a co-developer/solvent in the system.

Co-developer/solvent color developer co-monomers can be added incombination with a color forming agent at various ratios depending onthe application, desired color intensity, color development rate, colorhue, opacity and the like. Co-developer/solvents can be used from 99.9%total composition weigh to 0.1%. More usually, co-developer/solvents areused from between 99% to 1% by weight. Typically they are used between90% and 10%. Most often, they will find use from between 80% and 20% byweight total composition.

Of interest are additional solvents that do not block the ascendingtemperature color development provided by co-developer/solvent compoundsyet provide for lowering or raising the temperature transition of agiven ascending color change formulation. Additional non-interferingsolvents can be mineral oils, low temperature waxes, other branched ornon-branched hydrocarbons and the like.

Temperature post adjusting addition solvents can be added at percentagesthat promote a desired temperature threshold response of interest. Theycan be added and can be effective from 0.0001% by weight to a solublemonomer composition to greater than 90% by weight. Often, solventadditives will be added from between 0.001% up to 80% by weight. Moreoften modulating additives will be added from between 0.01% up to 70% byweight. Typically, modulating additives will find use from between 0.1%and up to 50% by weight and most often, modulating additives will beuseful between 1% and 25% by weight.

Additive Hysteresis Compounds for Ascending and Descending Color Change:

Compositions described herein may further benefit by adding solventcomponents that can be used to promote temperature hysteresis betweenthe ascending temperature and descending temperature. Compounds ofinterest include, but are not limited to: stearyl 2-methylbenzoate,cetyl 4-tert-butylbenzoate, behenyl 4-cyclohexylbenzoate, myristyl4-phenylbenzoate, lauryl 4-octylbenzoate, hexyl 3,5-dimethylbenzoate,stearyl 3-ethylbenzoate, butyl 4-benzylbenzoate, octyl3-methyl-5-chlorobenzoate, decyl 4-isopropylbenzoate, stearyl4-benzoylbenzoate, stearyl 1-naphthoate, cetyl phenylacetate, stearylphenylacetate, phenyl 4-tert-butylbenzoate, 4-chlorobenzyl 2-methylbenzoate, stearyl 4-chlorobenzoate, myristyl 3-bromobenzoate, stearyl2-chloro-4-bromobenzoate, decyl 3,4-dichlorobenzoate, octyl2,4-dibromobenzoate, cetyl 3-nitrobenzoate, cyclohexyl 4-aminobenzoate,cyclohexylmethyl 4-amino benzoate, cetyl 4-diethyklaminobenzoate,stearyl 4-aminobenzoate, decyl 4-methoxybenzoate, cetyl4-methoxybenzoate, stearyl 4-methoxybenzoate, octyl 4-butoxybenzoate,cetyl 4-butoxybenzoate, 4-methoxybenzyl benzoate, cetyl p-chlorophenylacetate, stearyl p-chlorophenylacetate, decyl3-benzoylpropionate, cyclohexyl 2-benzoylpropionate, myristyl benzoate,cetyl benzoate, stearyl benzoate, 4-chlorobenzyl benzoate, benzylcinnamate, cyclohexylmethyl cinnamate, benzyl caproate, 4-chlorobenzylcaprate, 4-methoxybenzyl myristate, 4-methoxy benzyl stearate, benzylpalmitate, 4-nitrobenzyl stearate, neopentyl caprylate, neopentyllaurate, neopentyl stearate, neopentyl behenate, cyclohexyl laurate,cyclohexyl myristate, cyclohexyl palmitate, cyclohexylmethyl stearate,2-cyclohexyl ethyl stearate, stearyl cyclo hexylpropionate,3-phenylpropyl stearate, 4-methoxybenzyl caproate, 4-methoxybenzylcaprate, 2-chlorobenzyl myristate, 4-isopropylbenzyl stearate, phenyl11-bromolaurate, 4-chlorophenyl 11-bromolaurate, didecyl adipate,dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyladipate, dibenzyl sebacate, distearyl tere-phthalate, dineopentyl4,4′-diphenyldicarboxylate, dibenzyl azodicaroboxylate, trilaurin,trimyristin, tristearin, dimyristin and distearin.

Standard and Non-Standard Micro-Encapsulation Processes:

Microencapsulation may be whereby surrounding or enveloping onesubstance within another substance on a very small scale, yieldingcapsules ranging from less than one micron to several hundred microns insize. Microcapsules may be spherically or otherwise shaped, with adefined wall surrounding the core, while others are asymmetrically andvariably shaped, with a quantity of smaller droplets of core materialembedded throughout the microcapsule. Multiple state types may bemicroencapsulated (solids, liquids, and gases.

Tunable compositions can be micro-encapsulated or non-micro-encapsulateddepending on the application of interest. Encapsulate species providethe inherent robustness for many matrices or mediums such as plastics,certain paints, or robust coatings. Un-micro-encapsulated speciesprovide a lower cost means to utilize said compositions where thecompositions can be administered to a product application in fewer lestcostly steps. Various permutations of encapsulated on un-encapsulatedtunable color generation compositions can be utilized. By way ofexample, but not limitation, developers and color formers can both beun-encapsulated. Alternatively, the developer can be encapsulated whereas the color former may be un-encapsulated. In another example, thedeveloper may be un-encapsulated whereas the color former may beencapsulated. In addition, varying degrees of encapsulation may beutilized by one component or another.

Microencapsulation may be achieved by a various standardized andnon-standardized techniques depending on the application of interest.Compositions may be microencapsulated with the intention that the corematerial be confined within capsule walls for a specific period of time.Alternatively, core materials may be encapsulated so that the corematerial will be released either gradually through the capsule walls,known as controlled release or diffusion, or when external conditionstrigger the capsule walls to rupture, melt, or dissolve.

Core materials can include, but are not limited to: the activeingredient or agent, fill, payload, nucleus, or internal phase. Thematerial encapsulating the core is referred to as the coating, membrane,shell, or wall material. Microcapsules may have one wall or multipleshells arranged in strata of varying thicknesses around the core.

Microencapsulated materials are utilized in agriculture,pharmaceuticals, foods, cosmetics and fragrances, textiles, paper,paints, coatings and adhesives, printing applications, safetyapplications, rapid temperature monitoring, advertising and promotion,low temperature indication, high temperature indication, toyapplications, publishing, games, and a wide range other industries andmarkets.

Carbonless copy paper applications may involve microencapsulatedcolorless ink that is applied to the top sheet of paper, and a developeris applied to the subsequent sheet. When pressure is applied by writing,the capsules break and the ink reacts with the developer to produce thedark color of the copy.

Others have referred to the use of microencapsulated materials toenhance the properties of finished goods. An increasingly importantapplication utilizes the incorporation of microencapsulated phase changematerials. Phase change materials absorb and release heat in response tochanges in environmental temperatures. Phase change materials can bepurchased from a wide range of chemical vendors (e.g. MicroteckCorporation or Bay Materials LLC). With increasing temperatures, thephase change material melts, absorbing excess heat, and feels cool.Conversely, as temperatures fall, the phase change material releasesheat as it solidifies, and feels warm. This property ofmicroencapsulated phase change materials can be harnessed to increasethe comfort level for users of sports equipment, military gear, bedding,clothing, building materials, and many other consumer products.

Active compositions and agents can be encapsulated to be released overtime, allowing farmers to apply the pesticides less often rather thanrequiring very highly concentrated and perhaps toxic initialapplications followed by repeated applications to combat the loss ofefficacy due to leaching, evaporation, and degradation. Protecting theactive compositions from full exposure to the elements lessens the riskto the environment and those that might be exposed to the chemicals andoften provide for a more efficient deployment.

A wide range of food additives, pharmaceuticals, medications, activecompositions, sensitizers, dyes, leuco dyes, diacetylenic monomers,polydiacetylenic materials, polymers in general, pesticides,micro-organisms, flavors, fragrances, stimulants, ingestibles,non-ingestibles, drugs, oxidants, anti-oxidants, and the like can bemicroencapsulated alone or in combination with the active optical changeagents describe herein.

Microencapsulation processes can be categorized by chemical processesand mechanical or physical processes including, but not limited to bulkfluid processes, phase separation processes, chemical processes,mechanical shear processes, milling processes, and commerciallyavailable processes. Compositions discussed herein can bemicroencapsulated using coacervation, interfacial polymerization,polymer-polymer incompatibility, phase separation processes,oil-in-water encapsulation, centrifugal processes, high-shear processes,mechanical drying processes, fluid bed coating, Wusrster processes,centrifugal extrusion, ultrasonication/coating, rotational suspension,double wall micro-encapsulation, chemical silanization processes,liposomal encapsulation, in-line printing/layering processes,heat/chilling cycling, embedding, in-situ polymerization,urea-formaldehyde systems, melaine formaldehyde systems, impregnation,particle coating, and a variety of other micro-particleformation/microencapsulation processes or the like.

Complex coacervation can be employed to provide capsules for use incontrolled dry delivery, fragrance samplers, pesticides and cosmeticingredients. Complex coacervation systems are one of the largestpractical applications of products of microencapsulation. In the complexcoacervation process gelatin having a high iso-electric point and gumarabic containing many carboxyl groups are added to a core-containingsuspension at relatively low pH above 35° C. The gelatin and gum Arabicreact to form microdroplets of polymer coacervate which separate. Thewall can be subsequently hardened by several means such as by theaddition of formaldehyde or glutaraldehyde. In the final steps, thesuspension of microcapsules is cooled and the pH raised after which thesuspension is filtered leaving the microcapsules on the filter media.Many variations of complex coacervation are known as well ascombinations of polymers. Complex coacervation can employed toencapsulate various tunable compositions describe herein.

Substrate Types Utilized for Coating with Tunable Compositions:

Tunable color change compositions can be applied and utilized with awide range of substrates (indicating substrates). Indicating substratecompositions include but are not limited to paper, plastic, hardsurfaces, soft surfaces, stiff or rigid surfaces, compliant surfaces,printed surfaces, printable surfaces, transparent surfaces,semi-transparent surfaces, opaque surfaces, non-transparent surfaces,skin, finger nails, molded surfaces, flexo-graphic printing surfaces,foam surfaces, expanded plastic surfaces, insulating surfaces,conducting surfaces, conducting ink surfaces, and the like. A substratecomposition can be comprised of thick or thin materials ranging inthickness from 1 nanometer to 100 centimeters. Often thicknesses willrange from 10 nanometers to 10 centimeters. More often substratessuitable for indicating compositions will range from 1 micron to 1centimeter. Typical substrates will range from 10 microns to 5millimeters and most often in the range between 0.1 millimeters and 1.0millimeters.

Color Formers, Compatible Thermochromic Dye Compounds:

A variety of different color former components may be employed,including thermochromic dyes. Thermochromic dyes and colorants ofinterest can be added to the composition formulation to serve as anindicating means to show that a particular composition has beentemperature activated for optimal use. Temperature ranges forthermochromic transitions can be below freezing to above boilingdepending on the intended use of the thermochromic compositionapplication. Thermochromic dyes can find use in a variety ofcompositions and applications and formats. Thermochromic dyes caninclude but are not limited to compounds including:bis(2-amino-4-oxo-6-methylpyrimidinium)-tetrachlorocuprate(II);bis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorod-icuprate(II);cobalt chloride; 3,5-dinitro salicylic acid; leuco dyes; spiropyrenes,bis(2-amino-4-oxo-6-methylpyrimidinium) tetrachlorocuprate(II) andbis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorodicuprate(II),benzo- and naphthopyrans (Chromenes), poly(xylylviologen dibromide,di-beta-naphthospiropyran, Ferrocene-modified bis(spiropyridopyran),isomers of1-isopropylidene-2-[1-(2-methyl-5-phenyl-3-thienyl)ethylidene]-succinicanhydride and the Photoproduct7,7adihydro-4,7,7,7a-tetramethyl-2-phenylbenzo[b]thiophene-5,6-dicarboxylicanhydride, micro-encapsulated dyes, precise melting point compositions,infra-red dyes, spirobenzopyrans, spironnapthooxazines, spirothopyranand related compounds, leuco quinone dyes, natural leuco quinone,traditional leuco quinone, synthetic quinones, thiazine leuco dyes,acylated leuco thiazine dyes, nonacylated leuco thiazine dyes, oxazineleuco dyes, acylated oxazine dyes, nonacylated oxazine leuco dyes,catalytic dyes, combinations with dye developers, arylmethanephthalides, diarylmethane phthalides, monoarylmethane phthalides,monoheterocyclic substituted phthalides, 3-hetercyclic substitutedphthalides, diarylmethylazaphthalides, bishetercyclic substitutedphthalides, 3,3-bisheterocyclic substituted phthalides, 3-heterocyclicsubstituted azaphthalides, 3,3-bisheterocyclic substitutedazaphthalides, alkenyl substituted phthalides, 3-ethylenyl phthalides,3,3-bisethylenyl phthalides, 3-butadienyl phthalides, bridgedphthalides, spirofluorene phthalides, spirobensanthracene phthalides,bisphthalides, di and triarylmethanes, diphenylmethanes, carbinol bases,pressure sensitive recrcording chemistries, photosensitive recordingchemistries, fluoran compounds, reaction of keto acids and phenols,reactions of keto acids with 4-alkoxydiphenylamines, reactions of ketoacids sith 3-alkoxdiphenylamines, reactions of 2′-aminofluorans witharalkyl halides, reaction of 3′-chlorofluorans with amines, thermallysensitive recording mediums, tetrazolium salts, tetrazolium salts fromformazans, tetrazolium salts from tetazoles, and the like.

Other thermochromic dyes of interest include leucodyes including colorto colorless and color to color formulations,vinylphenylmethane-leucocynides and derivatives, fluoran dyes andderivatives, thermochromic pigments, micro and nano-pigments, molybdenumcompounds, doped or undoped vanadium dioxide, indolinospirochromenes,melting waxes, encapsulated dyes, liquid crystalline materials,cholesteric liquid crystalline materials, spiropyrans, polybithiophenes,bipyridine materials, microencapsulated, mercury chloride dyes, tincomplexes, combination thermochromic/photochromic materials, heatformable materials which change structure based on temperature, naturalthermochromic materials such as pigments in beans, various thermochromicinks sold by Securink Corp. (Springfield, Va.), Matusui Corp., LiquidCrystal Research Crop., or any acceptable thermochromic materials withthe capacity to report a temperature change or can be photo-stimulatedand the like. The chromic change agent selected will depend on a numberof factors including cost, material loading, color change desired,levels or color hue change, reversibility or irreversibility, stability,and the like.

Alternative thermochromic materials can be utilized including, but notlimited to: light-induced metastable state in a thermochromic copper(II) complex Chem. Commun., 2002, (15), 1578-1579 under goes a colorchange from red to purple for a thermochromic complex,[Cu(dieten)2](BF4)2 (dieten=N,N-diethylethylenediamine); encapsulatedpigmented materials from Omega Engineering Inc.;bis(2-amino-4-oxo-6-methyl-pyrimidinium)-tetrachlorocuprate(II);bis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorod-icuprate(II);cobalt chloride; 3,5-dinitro salicylic acid; leuco dyes; spiropyrenes,bis(2-amino-4-oxo-6-methylpyrimidinium)-tetrachlorocuprate(II);bis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorod-icuprate(II);cobalt chloride; 3,5-dinitro salicylic acid; leuco dyes; spiropyrenes,bis(2-amino-4-oxo-6-methylpyrimidinium) tetrachlorocuprate(II) andbis(2-amino-4-chloro-6-methylpyrimidinium) hexachlorodicuprate(II),benzo- and naphthopyrans (Chromenes), poly(xylylviologen dibromide,di-beta-naphthospiropyran, Ferrocene-modified bis(spiropyridopyran),isomers of1-isopropylidene-2-[1-(2-methyl-5-phenyl-3-thienyl)ethylidene]-succinicanhydride and the Photoproduct7,7adihydro-4,7,7,7a-tetramethyl-2-phenylbenzo[b]thiophene-5,6-dicarboxylicanhydride, and the like. Encapsulated leuco dyes are of interest sincethey can be easily processed in a variety of formats into a plastic orputty matrix. Liquid crystal materials can be conveniently applied aspaints or inks to surfaces of color/shape/memory composites.

Thermochromic color to colorless options can include by way of example,but not by limitation: yellow to colorless, orange to color less, red tocolorless, pink to colorless, magenta to colorless, purple to colorless,blue to colorless, turquoise to colorless, green to colorless, brown tocolorless, black to colorless. Color to color options include but arenot limited to: orange to yellow, orange to pink, orange to very lightgreen, orange to peach; red to yellow, red to orange, red to pink, redto light green, red to peach; magenta to yellow, magenta to orange,magenta to pink, magenta to light green, magenta to light blue; purpleto red, purple to pink, purple to blue; blue to pink; blue to lightgreen, dark blue to light yellow, dark blue to light green, dark blue tolight blue; turquoise to light green, turquoise to light blue, turquoiseto light yellow, turquoise to light peach, turquoise to light pink;green to yellow, dark green to orange, dark green to light green, darkgreen to light pink; brown and black to a variety of assorted colors,and the like. Colors can be deeply enriched using fluorescent andglow-in-the-dark or photo-luminescent pigments as well as related coloradditives.

Reversible and irreversible versions of the color change agent can beemployed depending on the desired embodiment of interest. Reversibleagents can be employed where it is desirable to have a multi-use effector reuse the color change effect. For example, products with continuedand repeated use value will find utility of a reversible color changecomponent comprising the final embodiment. In this case it would bedesirable to utilize a reversible thermochromic or luminescent materialwhich can be repeated during usage. In another example, it may bedesirable to record a single color change permanently. In this case, itwould be desirable to utilize a thermochromically irreversible materialwhich changes from one color to another giving rise to a permanentchange and indicating that the composition should be discarded afteruse.

Luminescent or fluorescent pigments can be used in conjunction withco-topo-chemical polymerization compositions. Non-visible spectrumfluorescent dyes can be obscured by an one color of a diacetyleniccomposition or other thermochromic dye such that when a temperaturetriggering event occurs, the fluorescent signal becomes visible whenutilizing the corresponding wavelength to reveal the fluorescent dyecomposition.

Natural Food-Grade Descending Color Developers:

Compositions disclosed include carnauba wax as a novel natural singleand food grade single component co-developer-solvent that can be fordescending color development. Carnauba wax contains mainly esters offatty acids (80-85%), fatty alcohols (10-16%), acids (3-6%) andhydrocarbons (1-3%). Specific for carnauba wax is the content ofesterified fatty diols (about 20%), hydroxylated fatty acids (about 6%)and cinnamic acid (about 10%). Cinnamic acid, an antioxidant, may behydroxylated or methoxylated.

Good Emulsification Characteristics Food Grade

Carnauba wax can produce a glossy finish and as such is used inautomobile waxes, shoe polishes, food products such as candy corn,instrument polishes, and floor and furniture polishes, especially whenmixed with beeswax. It is used as a coating on dental floss. Use forpaper coatings is the most common application in the United States. Itis the main ingredient in surfboard wax, combined with coconut oil.

Because of its hypoallergenic and emollient properties as well as itsshine, carnauba wax appears as an ingredient in many cosmetics formulaswhere it is used to thicken lipstick, eyeliner, mascara, eye shadow,foundation, deodorant, various skin care preparations, sun carepreparations and the like.

Natural co-developer-solvents for descending color development can beused from 99.9% total composition weigh to 1%. More usually,co-developer/solvents are used from between 99% to 1% by weight.Typically they are used between 95% and 5%. Most often, they will finduse from between 90% and 20% by weight total composition.

Natural co-developer-solvents provide for low to high temperature rangereversible descending temperature color change compositions. By way ofexample, but not limitation, co-developer-solvents can be formulatedusing analog compositions of carnauba wax. Longer chain alcohol and orester compounds can be separated or added during the processing andpurification phase of preparing carnauba wax.

Carnauba wax and other related natural formulations can be used toproduce reversible color change compositions from below 0° C. to above150° C. Commonly commercially available leuco dye compositions aretypically limited to 70° C. and primarily include synthetic meltingpoint compositions and developers.

Natural Food-Grade Ascending Color Developer:

Compositions disclosed include glycerol monostearate wax as a novelnatural and food grade single component co-developer-solvent that can befor descending color development. Glycerol monostearate, popularly knownas GMS is an emulsifier compound. GMS is a colorless, odorless andsweet-tasting flaky powder that is hygroscopic. It occurs naturally inthe body and in fatty foods. It is formed during the breakdown(metabolism) of fats in the body.

A food additive used as a thickening, emulsifying, anti-sticking,anti-stalant agent; emulsifying agent for oils, waxes and solvents;protective coating for hygroscopic powders; solidifier and controlrelease agent in pharmaceuticals; resin lubricant. Used in cosmetics andhair care products. GMS is largely used in baking preparations to add“body” to the food. It is responsible for giving ice creams and whippedcreams its smooth texture.

Natural co-developer-solvents for ascending color development can beused from 99.9% total composition weigh to 1%. More usually,co-developer/solvents are used from between 99% to 1% by weight.Typically they are used between 95% and 5%. Most often, they will finduse from between 90% and 20% by weight total composition.

Additional Developers:

A range of alternate developers may be employed for various applicationsand at different ratios alone or in combination with naturalco-solvent-developers described depending on the intended use. Alternatedevelopers included but are not limited to: tert-butylphenol,nonylphenol, dodecyl phenol, styrenated phenols,2,2-methylene-bis-(4-methyl-6-tert-butylphenol), .alpha.-naphthol,.beta.-naphthol, hydroquinemonomethyl-ether, guaiacol, eugenol,p-chlorophenol, p-bromophenol, o-chlorophenol, o-bromophenol, o-phenylphenol, p-phenyl phenol, p-(p-chlorophenyl)-phenol,o-(o-chlorophenyl)-phenol, p-methyl hydroxy benzoate, p-ethyl hydroxybenzoate, p-octyl hydroxy benzoate, p-butyl hydroxy benzoate, p-octylhydroxy benzoate, p-dodecyl hydroxy benzoate, 3-iso-propyl catechol,p-tert-butyl catechol, 4,4-methylene diphenol,4,4-chio-bis-(6-tert-butyl-3-methyphenol),1,1-bis-(4-hydroxyphenol)-cyclohexane,4,4-butylidene-bis-(6-tert-butyl-3-methylphenol, bisphenol A, bisphenolS, 1,2-dioxynaphtaleine, 2,3-dioxynaphthalein, chlorocatechol, bromocatechol, 2,4-dihydroxybenzophenon, pheno phtalein, o-cresol phthalein,methyl protocatechinate, ethyl protocatechinate, propylprotocatechinate, octyl protocatechinate, dodecyl protocatechinate,2,4,6-trioxymethyl benzene, 2,3,4-trioxyethyl benzene, methyl gallicate,ethyl gallicate, propyl gallicate, butyl gallicate, hexyl gallicate,octyl gallicate, dodecyl gallicate, cetyl gallicate, stearyl gallicate,2,3,5-trioxynaphthalein, tannin acid and phenol resins.

Additives for Modulating Temperature Transitions:

Various oils including organic, natural, inorganic, and synthetic oilscan be added to diacetylenic compositions to up temperature shift ordown temperature shift the original diacetylenic composition's intrinsictemperature threshold. Oils can include, but are not limited to cornoil, various vegetables oils, nut oils, root oils, herbal oils, paraffinoils, greases, animal fats, natural extract oils, flavor based oils,aromatic based oils, industrial oils, and the like can be added toassist in modulating the temperature setting of a composition.

Oils based modulating additives or the like can be added at percentagesthat promote a desired temperature threshold response of interest.Modulating additives can be added and can be effective from 0.0001% byweight to a soluble monomer composition to greater than 90% by weight.Often, modulating additives will be added from between 0.001% up to 80%by weight. More often modulating additives will be added from between0.01% up to 70% by weight. Typically, modulating additives will find usefrom between 0.1% and up to 50% by weight and most often, modulatingadditives will be useful between 1% and 25% by weight.

Additives Including Printing Vehicle Additives For Post ModulatingTemperature Transitions:

Constituents may be added to printing vehicles that may be utilized toadjust the initial designated temperature of a formulated thermochromiccomposition. Resin constituents can include acids, bases, hardeningagents, softening agents, hydrating agents, dehydrating agents, effectoragents, phase shifting agents or the like.

Temperature post modulating additives or the like can be added atpercentages that promote a desired temperature threshold response ofinterest. Modulating additives can be added and can be effective from0.0001% by weight to a soluble monomer composition to greater than 90%by weight. Often, modulating additives will be added from between 0.001%up to 80% by weight. More often modulating additives will be added frombetween 0.01% up to 70% by weight. Typically, modulating additives willfind use from between 0.1% and up to 50% by weight and most often,modulating additives will be useful between 1% and 25% by weight.

Optical Pattern and/or Message Development:

Optical patterns can be developed under triggering conditions usingoptical color change dye systems in combination with modeled substratesurfaces. An image can be generated by applying a pressure indicatingfilm over a substrate layer that has been pre-surface textured orpatterned. As temperatures are induced the dye layer initially comes incontact with the close proximity regions or features of the patternedsubstrate surface. An initial color change will occur in the dye layerthe emulates the upper surfaces of the substrate. As temperaturescontinues to increase, the dye layer may be forced in contact with lowerregions of the substrate surface texture. Images or patterns can appeardifferentially as a result of the final temperature induced between thetemperature indicating dye layer and the patterned or texturedsubstrate. Partial images can be made to occur at lower temperatures.More complete or developed images or messages can be made to appear atmedium pressures. Fully developed images or completed messages can bemade to appear at final desired induced temperature.

Novel Printing Approaches for Discrete Color/Pattern Development:

Inkjet printing, drop-on-demand printing, continuous inkjet printing,multi-color flexographic printing and the like can be utilized toselectively print one or more of a color former, sensitizer, augmentingagent, or color developer composition. Amounts of one or the othercomponent or another can be selectively printed whereby generating imagedevelopment processes in novel formats.

Transient Reversible Color Development:

Dissolved aqueous formulations of dissolved or ultra-fine aqueousdispersions comprising a color formation compound and a mild colordevelopment compound can be produced in situ where by color isimmediately developed in the dissolved or dispersed medium. Thedissolving and dispersing process may involve solubility mediators suchas low or high molecular weight polyethylene glycols.

When the pre-colored mixture/medium is applied to or printed on asubstrate and dried, the color formation and color development compoundsare dissociated so that the color is eliminated. In the dried uncoloredstate, each component however remains immediately proximal to isinteracting pair. Importantly, re-hydration or re-solubilizing theprinted surface gives rise to instant color development that willtransiently dissipate upon re-drying. The transient reversible colorchange can be systematically repeated numerous times. The color changecan be made permanent by adding fixation agent to the re-hydration orre-solubilizing composition.

Passive and Active Rfid Temperature Integrating Devices:

In certain embodiments, energies generated in RFID circuits can beutilized as a stimuli to selectively and locally induce an opticalchange in color change compositions. Highly sensitive and responsivecompositions can be printed selectively and adjoined with a passive oractive RFID devices such that radio wave stimuli sent to the RFID devicecan be utilized to induce a color change dependent response. Theresponse can be triggered in the RFID circuit for the purpose of addinga visual indication means to the RFID device which otherwise, would notonly be visible during and RFID tag usage event.

Anti-Oxidants/Preservatives:

Various antioxidant and/or preservatives may be included in compositionsof the invention. Examples of compounds having anti-oxidant and/orpreservative activity include, but are not limited to: water solubleantioxidants, such as ascorbic acid, cysteine hydrochloride, sodiumbisulfate, sodium metabisulfite, sodium sulfite and the like;oil-soluble antioxidants, such as ascorbyl palmitate, butylatedhydroxyanisole (BHA), butylated hydroxytoluene (BHT), lecithin, propylgallate, alpha-tocopherol, and the like; and metal chelating agents,such as citric acid, ethylenediamine tetraacetic acid (EDTA), sorbitol,tartaric acid, phosphoric acid, and the like.

Machine-Readable Chemistries and Device Configurations:

In certain embodiments, indicator compositions of the invention find usein machine-readable applications. Machine-readable chemistry and deviceconfigurations can include, but are not limited to, various printedbarcodes, Interactive barcodes, abuse security barcodes; 1D, 2D, and 3D;barcodes holographic barcodes, vision imaging systems, transientbarcodes, time-only barcodes, freshness indicating barcodes, shapememory bar codes, and a variety of other applications and formats.

Compositions herein can be formulated and utilized in a variety ofvisual, scanning, imaging, and machine readable processes as they relateto temperature monitoring algorithms. Messages or codes can be made toappear or disappear; parts or elements of graphics, symbols or codes canbe utilized to make the element, graphic, or code un-discernable orunrecognizable until that portion of the medium has changed withtemperature or the like.

Indicator compositions can be utilized in both visual and machine aidedformats. Visual readings are made with distinct visual determination ofa threshold color change that occurs. Machine aided formats are madeusing an optical or electrical interpreted change in a color hue orconductive characteristic in a co-topo-polymeric composition thatundergoes a state threshold change. By way of example, but notlimitation, a composition can be printed or formulated in a machineviewable format. A measurable reading may be taken of an initialcolorimetric state. A second or sequential reading can be measured asthreshold state occurs. During the transition from one state to anotherstate, an instrumented reading can be registered. The thresholdtransition can be measured against a calibrated reading such that thedegree or magnitude of the state threshold change can be recorded andmonitored. Recorded and monitored machine measurements can be displayedby instrumentation utilized in the machine aided format.

Machine readable/responsive barcodes can be utilized for determining thepresence of or responding to a temperature fluctuation, visible light,ultra-violet light, irradiation for applications such as foodsterilization including gamma and cobalt 60 irradiation levels,hydration, pressure changes, high pressure events including highpressure sterilization, contaminations such a heavy metal contamination,alcohol levels, poisons, chemical sensing, biological compositions,chemical reagents, non-specific analyte binding, specific analytebinding, gases, physical and mechanical responses, UV intensity, lightintensity, sanitization conditions, mechanical stress conditions,pressurization formats, oxidation state, optical bleaching, end-of-useindication, time, time and temperature, free radical content, hydrationstate, skin care health, medical sterilization, clinical health status,indicating sensors on food storage containers medical status, securityapplications, anti-tampering applications, and any of a number of othermeasurable indicia.

Machine readable codes for indicating time duration for productshelf-life and use indication can be accomplished using sensingcompositions that shift spectrally in response to ambient conditions andproduct storage.

Also of interest are barcodes embedded or obscured with an indicatorcomposition that is selectively revealed upon triggering at set pointsof co-topo-polymeric indicator.

A range of barcode languages can be utilized that can be partially offully associated with a composition and therefore act as a machinereadable indication means to measure and report the selectivefunctionality intended to comprise the co-topo-polymeric compositionused for indication. Barcode types include, but are not limited to anylanguage, a wide range in size and numbers of character, as well as thebarcode language of interest: 39, 93, 128A, 128B, 128C,

A standard barcode or UPC code can be obscured, coated, embedded in orover-laid by a mixed or single component chromic change agent. Part ofthe standard bar code can be clearly visible at the beginning of readingso as to generate an initial starting parameter set. Selective portionsof the barcode can be covered by discrete compositions that are set tochange color at pre-determined temperature exposures. As the barcode isplaced on a product type at a lowered temperature the chromic changeagent can be activated. On activation, pre-determined elements of thecode will be obscured by the optical density of the chromic change agent(i.e., the indicator composition). The optical density of the barcodewill be set such that a barcode reader will not be able register theobscured portion/bars that represent a specific code sequence. As thebarcode/product is raised in temperature and as pre-selected temperatureare achieved and exposed, a pre-determined section of bar code will berevealed (reversibly or irreversibly depending on the nature of thechromic change agent selected). As each temperature threshold isachieved during the temperature exposure process, eachpre-determined/coated barcode region will become machine readable. Insome instances, an indicator may be configured as a linear segmentedbarcodes that differentially respond to temperature and/ortime-temperature along their axis.

Non-readable or partially readable barcodes utilizing single or mixedcompositions (e.g., color former compositions) as the obscuring agentare readily scanned for activity or inactivity in part or in whole.

Compositions herein and other blue/black bar codes provide a uniqueoptical masking characteristic that makes a partially readable of fullynon-readable part or all of the modified bar code. In addition thetransition of a blue/black compositions and compounds to a red or orangehue including but not limited to light pink to dark red hues, providesfor high optical readability by most commercial barcode readers sincethe red, orange, pink or related hues are optically transparent to thered light sources utilized in standard barcode readers.

Readable barcode languages include but are not limited to: Morovia Code25, 11, 12B. 139. UPC-A, UPC-E, EAN-8, EAN-13, code 128b, USS 39, USD 3,3 of 9 code, code 39. hibcc. Java applet, logmars, full, symbology,industry 2 of 5, discrete, self checking codes, msi, plesssey,one-dimensional barcodes, two-dimensional barcodes, three-dimensionalbarcodes, halographic barcodes, luminescent barcodes, and the like.

Barcode formats of interest include, but are not limited to: Off to Onswitching barcodes; On to off switching barcodes; Codes 39 and 93 forembedded thermal messaging; various barcode geometries, such as planar,curved, round, etc.; barcodes configured for thermal delay for timetemperature coding; freshness indicating barcodes; time-only indicatingbarcode; etc.

In some instances, one may have re-programmable barcodes that can bere-set among, in between or adjacent to a bar code set throughre-printing a region of interest.

Time/Low, Medium, and High Temperature Recording Mediums:

Non-aggressive to aggressive adhesives and contact or non-contactcompositions can be used in combination with optical developmentpigmentation as controlled time-dependent activation mechanisms.Commercially available and unique adhesive compositions are disclosedthat initiate color development in amenable dried optical pigments.Depending on the aggressive or non-aggressive nature of the pigment,viscosities, additives, promoters, or inhibitors, the color developmentprocess can be accelerated to short time durations (hours), to mediumtime durations (days), longer time durations (weeks), and prolonged timedurations (months to years).

A wide range of different printed substrates can be utilized usingdifferent printing means such as ink jet printing, drop on demandprinting, flexographic printed, rotogravier printing, off-set printing,screen printing or the like. Papers, films, plastics, printed surfaces,metals, composites and a range of other substrates can be utilized.

Applications include, but are not limited to safety products, food,beverage, pharmaceutical, electronics, tickets, promotional,advertising, printing, industrial, commercial, military, procurement,cold chain monitoring, timing indicators for water filters, securitybadges and applications, security papers, security documentation bags,laser engraving applications, 3-D laser lithography, pharmaceuticalperishability monitoring, promotional-time sensitive coupons and productapplications, consumer products for various household applications,commercial sanitary products requiring inspection and replacement suchadd deodorizers and urinal screens, tamper evident applications,self-changing price labels, self-activating lottery tickets, timeindication for scholastic testing, inventory timing and control,expiration coupons, full color image development, high temperature/timeindication, medium temperature/time indication, low temperature/timeindication, product applications as applied to a wide range ofconsumable and non-consumable products, promotional and advertisingapplications, food safety and storage products, cooking indicator andsensor designs and manufacturing processes, photochromic,mechanochromic, hydrochromic technologies, pressure indicatingtechnologies, tactochromic technologies, time indicating technologies,temperature threshold monitoring technologies, sensing and reportingtechnologies, shape/memory plastics, thermal transfer plasticstechnology, novel material science formulations, thermal expansioncompositions, disposable thermometers and devices, various rapidtemperature monitoring sensors and compositions, novel technical colorchange dyes and printing applications, microwave cooking sensors andapplications, interactive machine sensor readable formats, ingestiblesapplications, packaging applications, label applications and constructs,and applications to various industries, product embodiments, and newproduct categories relating to consumer products, consumer care productsincluding any and all improvements and the like.

Low Temperature Ranges for Time and Time/Temperature DependentMonitoring:

Low temperature application ranges include ranges in particular forperishable items such as food, beverages, alcoholic beverages,pharmaceutical products, blood, bio-pharmaceutical products, sensitivechemistries, rare materials, biological specimens, virulent bacteria andvirus, DNA and RNA storage, and a number of other temperature sensitiveitems or products that require temperature history and storageconditions to be monitored and recorded. Low temperature applicationscan range from −200° C. to 25° C.

Medium temperature ranges for time and time/temperature dependent andmonitoring:

Medium temperature applications include ranges further for perishableitems that expire at elevated temperatures, warm holding temperatures,monitoring medium temperature processes for process validation andquality control, storage conditions, warming foods, monitoring plantgrowth conditions, monitoring environmental conditions and livingconditions, industrial applications including manufacturing processes,storage of explosives, monitoring shipping storage containers fromoverseas suppliers, monitoring logistics of foods and goods crosscountry, in-flight monitoring of air freighted goods, and the like.Medium temperature application can range from 26° C. to 60° C.

High Temperature Ranges for Time and Time/Temperature DependentMonitoring:

High temperature applications include ranges further for perishableitems that expire at elevated temperatures, hot holding temperatures,monitoring hot temperature processes for process validation and qualitycontrol, storage conditions, heated foods, monitoring high temperatureconditions, hot holding food service applications where time andtemperature monitoring is important, monitor food processes that requirelimited time exposure at elevated temperature for food preparation,re-heating applications, microwave cooking applications where foods needto be heated and maintained at elevated temperatures for complete andthorough cooking, monitoring environmental conditions and livingconditions, industrial applications including manufacturing processes,storage of military items, high temperature monitoring shipping storagecontainers from overseas suppliers, novel autoclave and sterilizationconditions, medical equipment sterilization, monitoring logistics offoods and goods cross country, in-flight monitoring of air freightedgoods, and the like. Medium temperature application can range from 61°C. to 600° C.

Activating Color Developing/Adhesive Layers and Compositions:

Solvent-based or other adhesive compositions can act as color developersdirectly with the color former to develop color without the use ofancillary or classic color developers. By way of example, but notlimitation, aggressive adhesives including Tesafix™ 4965 (Tesa AGQuickbornstr, 24 D-20253 Hamburg Germany) and related adhesive tapesincluded, but not limited to Tesafix™ 4972. Admixes of low volatilitysolvents that may be suspended in or comprising polyacrylic acids andacrylic acid esters and the like can be used directly with color formersin the system described herein.

Tesa 4965 is a double sided adhesive tape consisting of a transparentpolyester film and acrylic adhesive. The adhesive system is especiallyresistant to plasticizers and offers a secure bond even at elevatedtemperatures.

Main cited applications of Tesa 4965 include: mounting of ABS plasticparts in the car industry, self-adhesive mounting of rubber/EPDMprofiles, mounting of decorative profiles and mouldings in the furnitureindustry, and mounting of battery packs, lenses and touch-screens inelectronic devices. It was non-obvious that the commercially availableadhesive tape could be used as a practical, low cost, and commerciallyavailable color development laminate.

4965 is an 8.1 mil, double coated adhesive tape consisting of atransparent polyester film with a red polypropylene release liner. Theadhesive system is especially resistant to plasticisers and offers asecure bond even at elevated temperatures.

Polymeric Color Developers:

Polyacrylic acid and polyacrylic acid esters are of particular interestin their function as dual active adhesives and acidic characteristicsthat simultaneously can provide and assist as a color developer whendirectly reacted with color forming compositions.

A variety of small to large molecular weight polyacrylic acids (PAA) canbe utilized. The molecular weight determination, degree ofpolymerization, mobility, proton donating characteristics, adhesivebinding characteristics, melting point characteristics, phasetransition, density, molecular weight cutoff, degree of chemicalmodification, associated binding resin and the like can be used asmodification characteristics in the color development process.

Acrylic acid monomers, oligomers, low molecular weight polymers, mediummolecular weight polymers, and high molecular weight polymers act asboth adhesive constituents as well as polymeric color developers.Acrylic acid monomers to high molecular weight polymers greater inmolecular weight than 50,000,000 g/mol can be utilized. Usually,oligomeric compounds ranging in molecular weight from 500 g/mol to20,000,000 g/mol will find use. More usually, polymers from 1,000 to10,000,000 g/mol in size will find dual uses as developers and adhesivecomponents. Typically polymers from 2,500 to 5,000,000 will be mostoften used.

Adhesive Composition Components:

Adhesive composition components can find use including specialty tapes,repositionable tapes, packaging tapes, permanent labels, andpeelable/repositionable labels. Raw materials commonly used in theseapplications include hydrocarbon tackifiers, rosin esters, and resindispersions. These products promote tack and enhance adhesion to lowenergy surfaces. Additional composition components can includesurfactants, emulsifiers, thickening agents, stationary colorants,micro-spheres to promote removable adhesives, diluents, labeling agents,security tagging agents and the like.

Polymeric acidic compositions can be formulated alone or along withcorresponding esters to form adhesive compositions with specified colordevelopment characteristics described. Solvents and tackifying agentswill be added to the adhesive composition to provide pressure sensitiveadherent properties to the color developing adhesive.

Solvents can include, but are not limited to aqueous solvents, organicsolvents, low volatility organic solvents, and inorganic fluids. It ispreferable to select a solvent system that provides for adequateadhesive properties, is low in volatility so that its properties areonly nominally impacted with time and evaporation, serves to adequatelysolubilize the polymeric acid composition, and provides for mobility andinteraction with in the color development system, but does notcomplicate or negatively impact he color development process.

Tackifiers are added to ensure pressure sensitive and immediate contactbetween the color development adhesive composition and the color formingsubstrate layer. By way of example, but not limitation, tackifiers caninclude carboxylated monoesters of polyglycols, etc. A wide range ofsolvent and water based tackifiers are commercially available and can beutilized in the time-temperature indicating system.

Polymeric binders of the adhesive can be chosen from a large series ofpolymers. Polymers can be soluble and/or alkali-soluble and compatiblewith the used tackifier. Suitable water-soluble and alkali-solublepolymers are e.g., polyvinylpyrrolidone, polyacrylic acid,polymethacrylic acid, copolymers of acrylic acid with alkyl esters ofacrylic or methacrylic acid wherein the alkyl group comprises 1 to 4carbon atoms such as methyl acrylate and n-butyl acrylate, with theproviso that the acrylic acid content is at least above 70% in the caseof methyl acrylate and above 85% in the case of n-butyl acrylate,further copolymers of maleic acid and e.g. ethylene, vinyl methyl etherand vinyl acetate, dimethylhydantoin-formaldehyde resin and polyethyleneimine.

The polymerization of acrylic acid and of methacrylic acid and thecopolymerisation of these acids with lower alkyl esters of acrylic acid(methyl, ethyl, butyl) may be carried out in solution in water, inmethanol or in mixtures of both according to known polymerisationtechniques, e.g. according to the methods described in Houben-Weyl,“Methoden der organischen Chemie”, Makromolekulare Stoffe, vol. 14/1,pages 1018-1021, Georg Thieme Verlag, Stuttgart (1961). Polymerisationmay also occur according to known methods in a non-solvent, whereby thepolymer formed precipitates out of solution. In the same way emulsioncopolymerisation techniques may be applied when mixtures are used ofacrylic acid or methacrylic acid with alkyl esters thereof, wherein theratio of acid component is relatively low (30 to 55% by weight). Theratio of the amount of polymeric binder present to the amount oftackifier used can vary within very wide limits and depends among otherson the relative humidity interval in which the adhesive tape is to beused. Best results are attained, however, when the amount of tackifieris from 100 to 280% by weight relative to the amount of polymeric binderpresent.

Tackifying Agents, Resins, and Matrices:

Hydrocarbon resins as tackifiers are comprised from petroleum basedfeedstocks either aliphatic (C5), aromatic (C9), DCPD(dicyclopentadiene), or mixtures of these. C5, aliphatic Resins are sonamed because they are generally polymers of monomers with five carbons.Basic C5 aliphatic resins have Gardner colors between 1.5 and 6 (fromlight yellow to light brown) and are mostly used to tackify aliphaticpolymers, especially natural rubber, EVA, SIS and APO. Hydrogenated C5,Aliphatic Resins are basic C5 hydrocarbon tackifiers that have beenhydrogenated to improve their color and thermal stability.

C9, Aromatic Resins are so named because they are generally polymers ofnine-carbon aromatic monomers. They are based on aromatic feedstocksthat undergo very little refining prior to the polymerization of theresin. They are usually dark in color within typical Gardner color of 6to 10 (dark yellow to dark brown). They are used mainly in EVA-basedadhesives, contact adhesive for footwear, printing inks, sealants, andpaints. C9 liquid resins are especially useful in flooring adhesives. Asa class, C9 resins have a distinctive aromatic odor. There are twosub-categories of C9 aromatic tackifiers, each with distinctiveproperties.

Pure Monomer C9, Aromatic Resins are based on aromatic feedstocks thathave been highly purified prior to polymerization. These are usuallywater-white with excellent stability. The lower softening point (<100°C.) types are mainly used in EVA for book binding adhesives and toimprove creep resistance in HMA for diapers. The higher softening pointpure monomer resin types are useful as end-block re-enforcers (enhancecohesive strength) in styrenic block copolymers, SIS, SBS, and SEBS.

Hydrogenated C9, Aromatic Resins are produced through the controlledhydrogenation of basic or pure monomer aromatic resins. A hydrogenatedhydrocarbon tackifier resin is the best choice when color and stabilityare overriding concerns. Usually these resins are colorless(water-white) and are very stable to heat, weathering, and oxidation.Most are hypo-allergenic, with no skin-sensitization properties and areideally suited for adhesives used in the medical industry where theseconsiderations are critical.

C5/C9, Aliphatic/Aromatic Resins are C5 tackifiers co-polymerized witharomatic monomers. They are excellent tackifiers for use in EVA, SBS,and natural rubber polymers. They can also be used in SIS-based HMPSA toprovide low melt viscosities with an optimum balance between cohesionand adhesion. Sometimes the slightly aromatic modified C5 resins areused in APO to provide limited compatibility resulting in shorter opentimes. Darker colored, lower cost types are often used in packaging HMAbased on EVA. These resins are mostly C9-based co-polymerized with C5aliphatic monomers.

The multiple element simultaneous characteristic of intimate adhesion,direct color development ability, time-delayed activity of colordevelopment, optical clarity, and ability to be tuned and modifiedchemically provide for a broad platform of application as a new class ofcolor former/color developer systems described herein.

Alternatively, polymers containing acidic side chains comprisingmethacrylic acid, acryloyl chloride, acrylamine co-mixes, acrylateco-polymer admixes, sodium polyacrylate, propionic acid polymers,acryloyl groups, methacrylic acid derivatives, ethylacrylic acids can beutilized in addition to or in alone.

PAA can disperse the micro-crystals or micro-sand of calcium carbonate,calcium phosphate and calcium sulfate. Polyacrylic Acid is used as scaleinhibitor and dispersant for circulating cool water system, papermaking,weave, dyeing, ceramic, painting, etc. polyglycolic acid polymer asynthetic biodegradable polymer, monomeric diacetylenes,polydiacetylenic acid polymers, monomeric and polymeric bisphenol A,butylated hydroxyanisole (BHA also used as an anti-oxidant) monomers andpolymers thereof, butylated hydroxytoluene (BHT),

PAA based color developers can be dispersed, dissolved in, homogenizedin, solubilized in, or combined with low volatility solvents such thatthe acid donating properties of the acidic side chains are available toparticipate in charge transfer characteristics of color development witha particular color forming composition comprising the adhesive timeindicating system.

The addition of augmenting agents can be utilized to accelerate ordecelerate the color development process. Accelerating agents can becomprised of compositions that facilitate the breakdown ofencapsulation, semi-encapsulation, migration, or diffusion of one orboth color developer or color former during a time and/or temperaturemonitoring event.

Decelerating agents can be comprised of compositions that facilitate thestability of encapsulation, semi-encapsulation, migration, or diffusionof one or both color developer or color former during a time and/ortemperature monitoring event.

Accelerating agents can be added to a time and/or temperature indicatingcomposition from between 0.01% to 90%. More often accelerating agentswill be added between 0.1% and 50%. Usually accelerating agents willfind use between 1% and 30% by weight in the final concentration in atime indicating composition.

Decelerating agents can be added to a time and/or temperature indicatingcomposition from between 0.01% to 90%. More often decelerating agentswill be added between 0.1% and 50%. Usually decelerating agents willfind use between 1% and 30% by weight in the final concentration in atime indicating composition.

The time-temperature dependent system described can utilize individualtime dependent color development composition components andpredetermined ratios provides for a wide range of performancecapabilities for the system. Systems of interest can include one or moreof the following components:

-   Color developer: (cd)-   Color former: (cf)-   Encapsulating composition: (ec)-   Adhesive composition: (ac)-   Accelerating agent (aa)-   Decelerating agent (da)-   Blocking composition: (bc)

Passive and Active Modulating Agents and Matrices:

Passive and/or active modulating agents and matrices can be used tooffset, separate, control, modulate, accelerate, delay, attenuate, orpredictably influence the interaction between color former compositionsand color developer systems. The exact composition, thickness,concentration, and characteristic of modulating agent or substrate willdepend on the application and/or desired effect intended for aparticular application of interest.

Offset delay layers between the color former layer and the adhesivecolor development layer can be pressure actuated locally using a stylus,pencil or other pressure means such as a fingertip blunted object orsharpened object. The localized pressure can be used to induce alocalized adhesion and localized initiation of the time ortime-temperature dependent color development process. Messages can bewritten, dates applied, or other text or symbolic information noted andcorresponding color developed as result of localized contacts.

Blocking and modulating layers can include, but are not limited to:chemical, physical, films, adhesive layers, wax layers, diffusionlayers, porous layers melting layers, high viscosity layers and the likecan be utilized to block or delay the onset of color development as wellas be used to great differential time delays compared with directinteraction between the color forming layer and the developing layer.

In addition to acting as carrier matrices, purified or complexcompositions can act as a separation layer between the color forminglayer and the associated color development layer. By way of example, aprinted color-forming layer can be post coated with a hydrocarbon layer.The layer can act to delay the onset of color development when anactivating adhesive or other color development layer is placed inintimate contact with the hydrocarbon layer juxtaposed to thecolor-forming layer. Color development can occur as the colordevelopment agent in the adhesive layer migrates through the layer andsubsequently interacts with the color-forming layer to develop a color.

Passive and/or active modulating agents and matrices include, but notlimited to waxes, acrylics, plastic resins, carboxy methyl cellulose(CMC), printing varnishes, hydrocarbon layers, nitrocellulose, paraffin,microcrystalline waxes, natural waxes, clay coatings, coating resins,tapes, non-developer containing adhesives, particulate,micro-particulate, thin metal layers, plastic film layers, dried proteinlayers, dried cellulosic layers, spray coated layers, surfactant layers,emulsifiers, membranes, semi-permeable membranes, filters, transparentlayers, compliant layers, and the like.

Sharp melting point mediums, long chain amines, long chain carboxylicacids, long chain weak acid donors, charge carrying polymers, polymerizewaxes, alkylated polymers, polyenes, polyolefins, polyethylene glycols,polypropylene glycols and a wide range of other passive or activematrices can be utilized in the resin system to achieve a suitableaugmentation effect.

Clay coatings provide a protective, smooth printing surface on varioussubstrates natural papers. The base paper—used for consumer packaging orprinted marketing materials—must be coated to produce a surface that isbright white, opaque and smooth, with either a glossy or matte finish.This coating allows the base paper to receive high quality printing oftext and graphics, without bleeding or smudging. Clay coatings can bepurchased from commercial vendors (e.g. NuCoat Inc.)

Purified Hydrocarbon Carriers as Passive and Active Matrices:

Purified hydrocarbons, each of which can be used as a solvent tosolubilize monomeric color formers and yet not directly or on their owncause color development, can be selected as carriers that can affect thetemperature transition associated with color development resulting fromsolvating a color former and a developing adhesive layer or agent.Purified hydrocarbon carriers include, but are not limited to chainlengths of C10, C11, C12, C13, C14, C15, C16, C18, C19, C20, C21, C22,C23, C24, C25, C26, C27, C28, C29, C30 and longer synthetic and/ornaturally derived hydrocarbon chain lengths.

Similarly, longer hydrocarbon chain lengths can be used to mitigatecolor development at temperatures well below the melting transition ofthe hydrocarbon comprising the separation layer. Not until a thresholdtemperature above the melting or softening transition of the hydrocarbonlayer along with the combined interaction of the adhesive compositionwill the color developing adhesive composition give rise to anassociation with the color forming layer and initiate color development.

Layer thicknesses can range from 0.1 micron to over 2 millimeters.Usually, layers find practical use in between 0.5 microns and 1millimeter. More often, layers will range between 1 micron and 500microns. Most often, layers are formed and used between 10 and 100microns depending on the application of interest and time delay or colordevelopment onset delay of interest for a particular productapplication.

Microcrystalline Wax and Paraffin Bases for Color Former Dispersion:

Example high melting point paraffins:

Product Code Melt Point (° F.) Melt Point (° C.) IGI 1303A (AW5512) 15467.8 IGI 1380A 153 67.2 IGI 1260A 157 69.4Example mid melting point paraffins:

Product Code Melt Point (° F.) Melt Point (° C.) IGI 1239A 138 58.9 IGI1240A 136 57.8 IGI 1242A 139 59.4 IGI 1245A 140 60 IGI 1250A 142.5 61.4IGI 1302A (AW4212) 140 60 IGI 1343A 138 58.9Example low melting point paraffins:

Product Code Melt Point (° F.) Melt Point (° C.) IGI 1230A 130 54.4 IGI1236A 132 55.6Example microcrystalline waxes:

Melt Point Hardness Viscosity Color Packaged ° C./° F. @ 25° C. @ 100°C. D1500/D156 Forms MICROSERE 5788A 60/140 40 dmm 19 mm²/sec L0.5/— SlabMICROSERE 5701A 70/160 28 dmm 14 mm²/sec L0.5/— Slab MICROSERE 5714A70/160 28 dmm 14 mm²/sec L1.5/— Slab MICROSERE 5715A 77/170 28 dmm 16mm²/sec —/+16 Slab MICROSERE 5799A 77/170 28 dmm 16 mm²/sec L1.5/— SlabMICROSERE 5818A 83/181 18 dmm 16 mm²/sec L3.5/— Slab & Pellet MICROSERE5871A 83/181 18 dmm 16 mm²/sec L0.5/— Slab & Pellet MICROSERE 5890A83/181 18 dmm 16 mm²/sec —/+16 Slab & Pellet MICROSERE 5981A 84/183 14dmm 14 mm²/sec L0.5/— Slab, Pellet & Granule MICROSERE 5897A 87/188 18dmm 20 mm²/sec L0.5/— Slab, Pellet & Granule MICROSERE 5896A 87/188 18dmm 20 mm²/sec —/+16 Slab, Pellet & Granule MICROSERE 5901A 89/192  9dmm 15 mm²/sec L0.5/— Slab, Pellet & Granule MICROSERE 5999A 90/194  8dmm 20 mm²/sec L1.5/— Slab, Pellet & Granule MICROSERE 5909A 90/194  8dmm 20 mm²/sec L0.5/— Slab, Pellet & Granule MICROSERE 5910A 90/194  8dmm 20 mm²/sec —/+16 Slab, Pellet & GranuleRelevant applications for microcrystalline waxes:

Grade Melting Point Hardness Applications Type 1 - Laminating 54 to 76°C. 20-35 dmm Packaging Adhesives Cosmetics Rubber Candles Type 2 -Coating 76 to 85° C. 14-25 dmm Adhesives Packaging Chewing Gum InksPlastics Rubber Type 3 - Hardening 85 to 95° C. 6 to 14 dmm AdhesivesInks Chewing Gum Candles Specialty

Long Chain Alcohols As Color Former Carriers:

Unilin® Alcohols are available through Baker Hughes Inc., UNILINalcohols feature than other commercially available linear alcohols.Compared with conventional alcohol technology that has been limited tocarbon chain lengths of C30 or below, UNILIN Alcohols from BakerPetrolite are available with average chain lengths of C24 to C50. Meltpoints of UNILIN Alcohols products range from 78° C. to 106° C.Completely linear structure Fully saturated Higher molecular weights,Higher melting points, Greater crystallinity, and greater alcoholcontent UNILIN Alcohols are composed of approximately 80% primaryalcohol; the remaining 20% is saturated or chemically inactivehydrocarbons of the same molecular weight. The hydroxyl function of thealcohol is evenly distributed among all carbon chain lengths. UNILINalcohols from Baker Petrolite may be incorporated into a wide range ofchemical processes and formulations. They offer improved compatibilitywith other high molecular weight functional polymers when compared toshorter chain alcohols or non-functional hydrocarbons. Features benefitsof alcohol functionality include: Increased solubility in polar systemsCo-emulsifier for silicones reactive sites for derivatives Linear carbonbackbone: Compatible with hydrocarbons Solvent resistance in coatingsHard Controlled Mn (350-700) and narrow MWD: formulating flexibilityControllable melting point Low melt viscosity UNILIN® Alcohols fromBaker Petrolite are incorporated as intermediates into a wide variety ofindustrial chemical processes and applications. Chemical intermediatesfor oxidation, sulfation, amination, and esterification: additives foradhesive formulations additives for coatings/paints and toners Lubricityimprovers in plastics defoamer additives for pulp and paper systemscompatibility enhancers for silicone systems Intermediate for polyesterresins to reduce sensitivity to humidity

Reversible/Irreversible Co-Development Indicating Present and HistoricalTemperature:

Reversible color developer/solvents such a glycerol monostearate can beutilized as a reversible color developer along to develop color in acolor former type.

In the absence of an irreversible color developer such as an aggressiveadhesive layer the color generation process can proceed reversibly uponascending temperatures. An irreversible color developer can be appliedadjacent to or within the same indicating device or layer. During anascending temperature event, the color development process will beirreversibly recorded in the presence of the irreversible colordeveloper whereas reversible color development area will record onlypresent time temperature conditions. The presence of both reversible andirreversible color development process simultaneously within the samedevice or indicator has the significant advantage of providing bothhistorical temperature history as well as present temperature historyutilizing the same color former system and developer elements.

Alternatively, descending color change dye compositions can be developedusing the system described herein for irreversible or reversibletemperature indication for development recording temperature historieswhere it is important to indicate whether a product had been exposed toa low temperature threshold in contrast to a high temperature threshold.

Activation of Time-Temperature Color Development Process:

Activation or initiation of the time and temperature dependent colordevelopment process begins upon intimate interaction of essential systemcomponents. Activation can be accomplished manually by applying a labelcontaining one component to a substrate containing a second member. Bothmembers are required for initiation and color development. In a secondexample activation can begin upon label application and contact betweentwo members of the full color development pair by using automatedlabeling equipment.

Wrap around label applicators can be used for activation at the labelingpoint using labels constructed with one member of a color system on onesurface ant the other member on the opposing surface. During wrap aroundlabel application the bottom portion of a label will come in contactwith the second member to initiate the color development process.

Pull tab activation finds use where semi-manual activation approachesare desired. A pull tab can be used to separate the two component colordevelopment system such that when the separation tab is pulled, thepulling process draws one layer member in intimate contact with theother layer member. Activation begins during the adhesion process.

Blocking layers can be utilized where by the blocking layer keepsdormant and maintains separation between two layer components until anelevated temperature or time is achieve. When a threshold temperature isachieved thereby melting or diffusing the blocking layer, both colorformer and color developer layer are allowed to interact and the colordevelopment process can proceed above the designated temperature or atany point where the blocking layer is eliminated.

Pressure initiated activation can be utilized whereby pressure isrequired to force on layer of a pair in direct contact with the secondlayer to induce intimate contact. Off-setting spacers can be used toseparate one layer from the other. A gap can be placed between the twolayers filled by only air or a displacing composition. As presser isplaced on one layer, the second layer is forced to interact and initiatethe color development process.

Blister packing constructs can be utilized where by on member of anactivating pair can be placed distal to a second layer using adisplacing plastic indented structure. As the indented structure isdeformed or flattened, the deformation process forces both members ofthe color development pair to interact and initiate the colordevelopment process.

Bubble burst activation can be utilized whereby both members of a colordevelopment pair are separated by an air or gas pocket. Separation isdisrupted by pressing and rupturing the bubble. An added sound effectcan be elicited as an audio confirmation of initiating the colordevelopment process. Bubble separators can be further used to generatepatterns during multiple adjacent ruptures. Advertising or promotionalapplications will find use as arrays of bubble activating patterns canbe utilized.

Direct Thermal Label and Color Sensitive Medium Integration:

Completed constructs can be utilized whereby existing thermal papers,films, labels or substrates and carbonless papers, films, or substratescan be paired with an aggressive color developing adhesive describedherein. Commercially available thermal substrates and carbonlesssubstrates can be purchased and utilized in the system. Commerciallyavailable thermal substrates and carbonless substrates can be suppliedby but not limited to: Appleton Papers Inc., Fuji Films Corp., MicrotekCorporation, NuCoat Inc., NoCopi Technologies, Inc., Crayola Company,Elmers Inc., and Segan Industries, Inc., LCR Corp., TMC LLC, Rub andColor brand, Matsui Corp., Pilot Ink Crop., New Prismatic Corp., andother commercial providers of technical color change dyes and products.

As described in U.S. Pat. No. 4,822,770 carbonless copy paper isprepared by placing a first sheet of paper coated on one side with ahydrophilic colloid solution in which are dispersed microcapsules of oildroplets containing a colorless electron donor dye into contact with asecond sheet of paper coated with an absorbent and an electron acceptingcolor developer compound. The heat resistance and moisture resistance ofthe copy paper is substantially improved by adding to the hydrophiliccolloid solution a graft copolymer having a backbone of carboxymethylcellulose or gum arabic and side chains of polyacrylic acid orpolymethacrylic acid. The image response time of the second sheet can beimproved by adding pectin or sulfated starch to the coating. Substratessuch as these can be utilized in combination with aggressive colordeveloping adhesives to unexpected create time and time-temperatureindicators.

Likewise, adhesive color development laminates can be utilized to adjustthe intended color development threshold of existing direct thermallabels. By way of example, but not limitation, commercially existingdirect thermal label substrates including paper and plastic film types,can be up-shifted in temperature or down shifted. Up-shifting can beaccomplished by increasing the threshold properties of the directthermal composition (e.g. inducing a localized differential base or acidchange into the direct thermal composition. Downshifting the temperaturetransition of a direct thermal label composition can be accomplishedboth by an acid/base change locally as well introducing an increasedmobilization and solvation property in the direct thermal composition.

Direct thermal papers and films most readily adjusted will be those withthermal compositions and coating amenable to localized changes that canbe introduced by introduction and interaction of the adhesive overlay.The intended up-shift or downshift in thermal characteristics of thedirect thermal transfer substrate will depend on the intendedapplication of interest, the degree of temperature change intended andthe time intended for introducing and optical change in the substrate.

Similarly, a commercially available direct thermal coated substrate canbe converted into a time only indicating substrate depending upon thethermal coating composition and provided protective coating. Byadjusting the aggressive nature of the adhesive overlay, the solventcontent, the acid/basic nature of the adhesive employed and any intendedaugmenting agents comprising the adhesive composition, application ofthe adhesive laminate can be utilized for conversion of the substrate toshorter or longer duration time indicators.

Example direct thermal recording substrates available and useful fromAppleton Papers Inc. include:

Part Number Description 3802-0221 RESISTE 600-4.4 8 ⅞ 5 M 2137-0036RESISTE 200-3.1 61 9 M 4723-0086 RESISTE 500-3.4 9 ½ 1 M 4723-0044RESISTE 500-3.4 9 ¼ 9 M 3802-0227 RESISTE 600-4.4 7 6 M 3802-0080RESISTE 600-4.4 40 ½ 4.5 M 4723-0051 RESISTE 500-3.4 13 5/16 6 M3802-0182 RESISTE 600-4.4 13 13/32 9 M 4211-0016 RESISTE 800-7.2/T954 176.5 M 4723-0092 RESISTE 500-3.4 8 ¾ 9 M 3802-0224 RESISTE 600-4.4 1319/32 4.85 M 2137-0018 RESISTE 200-3.1 27 9 M 3802-0043 RESISTE 600-4.413 ⅜ 6 M 3802-0254 RESISTE 600-4.4 19 ⅞ 7 M 3802-0195 RESISTE 600-4.4 19½ 9 M 3802-0007 RESISTE 600-4.4 13 ½ 9 M 3802-0247 RESISTE 600-4.4 10 ¾7.778 M 3802-0167 RESISTE 600-4.4 16 ½ 1 M 2137-0026 RESISTE 200-3.110.5 M 3802-0256 RESISTE 600-4.4 16 15/16 9 M 4723-0058 RESISTE 500-3.49 ½ 6 M 3802-0145 RESISTE 600-4.4 26 ⅞ 6 M 4723-0042 RESISTE 500-3.4 16½ 9 M 4723-0002 RESISTE 500-3.4 24 ½ 6 M 3802-0142 RESISTE 600-4.4 5 3 M3802-0151 RESISTE 600-4.4 13 ½ 6 M 3802-0138 RESISTE 600-4.4 5 4.5 M3802-0000 RESISTE 600-4.4 3802-0130 RESISTE 600-4.4 4 ¾ 4.5 3802-0065RESISTE 600-4.4 12 ¼ 6 M 2137-0022 RESISTE 200-3.1 50 6.667 M 4723-0087RESISTE 500-3.4 39 ¼ 9 M 4723-0003 RESISTE 500-3.4 48 ½ 6 M 3802-0106RESISTE 600-4.4 13 1 M 4211-0024 RESISTE 800-7.2/T954 13 1 M 2137-0028RESISTE 200-3.1 53 ¼ 9 M 4211-RL RESISTE 800-7.2/T954 3802-0116 RESISTE600-4.4 15 4.5 M 3802-0238 RESISTE 600-4.4 5 13/16 6 M 3802-0250 RESISTE600-4.4 16 ¾ 5.2 M 7041-SH 62 C1S PEARLESCENT LABEL 3609-SH C1S CREAMLABEL 3659-0087 T1062A OPTIMA LABEL 40″ 9 M 3796-RL C1S PK FLUOR LABEL4946-RL BASE-COATED LABEL STOCK - 13 CM 7377-0000 BLADE COAT THERMALLABEL 0000-3909 C1S #270 CRM LABEL 25 × 38 3659-0033 T1062A OPTIMA LABEL30 ¾″ 6 M 3659-0065 T1062A OPTIMA LABEL 40″ 6 M 4946-0001 BASE-COATEDLABEL STOCK - 13 CM 3659-0063 T1062A OPTIMA LABEL 8 ½″ 6 M 3608-0009 C1SCAN LABEL 38 × 50 3659-0101 T1062A OPTIMA LABEL 60 ¾″ 9 M 3659-0015T1062A OPTIMA LABEL 53″ 4.5 M 5194-0001 BARRIER LABEL 62#FDA 20.5 × 23.57041-0000 62 C1S PEARLESCENT LABEL 3608-0000 C1S CAN LABEL 7377-RL BLADECOAT THERMAL LABEL 3608-RL C1S CAN LABEL 3659-0128 T1062A OPTIMA LABEL60 ¾ 12 M 3659-0169 T1062A OPTIMA LABEL 52″ 12 M 3659-0155 T1062A OPTIMALABEL 24″ 3 M 3610-RL C1S IVORY LABEL 3659-0119 T1062A OPTIMA LABEL 13″9 M 3823-RL SC SP TAN LABEL 3608-0010 C1S CAN LABEL 25 × 38 3659-0165T1062A OPTIMA LABEL 61″ 9 M 3796-SH C1S PK FLUOR LABEL 3796-0000 C1S PKFLUOR LABEL 0000-1227 150 AP LABEL PLT 61″ 9.666 M. 4946-0000BASE-COATED LABEL STOCK - 13 CM 3801-SH C1S SP BUF LABEL 3659-0034T1062A OPTIMA LABEL 38 ⅝″ 9 M 7041-RL 62 C1S PEARLESCENT LABEL 0000-2711C1S 259 GLD AP LABEL 26 × 20 3801-RL C1S SP BUF LABEL 5021-0001 GENDATALABEL-2.1 53 3 M 3609-RL C1S CREAM LABEL 3659-0105 T1062A OPTIMA LABEL26 ½″ 6 M 3659-0085 T1062A OPTIMA LABEL 61 ¼″ 9 M

Time based color development process for devices, sensors, and productsdescribed above can range from seconds to years depending on theintended application of interest, compositions comprising said devices,delay layers employed and the like. Usually, time based applicationswill range from minutes to months. More usually, intended applicationswill utilize compositions and constructs that will give an observablecolor development in the range of hours to weeks.

Spot Color Developing Adhesives:

Printable spot color development adhesives were can be prepared usingcolor developing polymeric and non-polymeric color developers,tackifying compounds, and ancillary binding agents and resins. Spotprinted adhesives have the advantage over flood coated adhesive inmaking time and time temperature indicating constructs in that the spotadhesive can be selectively printed, pattern, and positioned inselective areas for desired and enhanced effects. Likewise, printed spotadhesives comprising color decaying compositions can be formulated usingbasified compositions under similar means.

Time-Temperature and Temperature Thermometers:

Visual read thermometers and sensors can be produced usingtime-temperature and time based color forming and color developingcompositions. Constructs comprising thermometers can include a colorforming layer on a substrate, a delay or temperature responsive blockinglayer, and a pre-adhered color developing layer. The selection ofcomponents can be used to pre-set the time-temperature and temperaturetriggering temperature threshold of the thermometer.

In particular, the blocking layer positioned between the color forminglayer and the adhered color developing layer can be formulated with ablocking compound that responds to and transforms to a permeable layerat a specified temperature. By way of example, the blocking layer may bea sharp melting point medium such as a wax, paraffin, or othercommercially available sharp melting point medium. Upon melting,softening, or becoming permeable, the blocking layer will no longer beable to block or inhibit interaction between the color developmentsystem and an irreversible color will develop at the pre-determinedtemperature setting.

A time-delay can be introduced into the thermometer by adjusting thediffusion path, permeability characteristics of the blocking layer,composition of the color forming layer, and composition of the colordeveloping layer. Time delays will typically be in the shorter durationstages from less than a second to several hours. More often time delayswell be utilized in the range from a few seconds to an hour depending onthe application of interest.

Thermometers can be produced to using the system to measure temperaturesranging from sub-freezing to over 1,000° C. Usually, temperature rangewill be in the freezer range starting at −5° C. and cover ranges incooking and product preparation ranges up to 500° C. More oftentemperature ranges for thermometers will find use in the refrigeratorrange from 10° C. to 250° C.

Reversible Re-Activation Using Color Eliminating Systems:

Microencapsulated reversible leuco dye compositions can be converted toirreversible time and or temperature monitoring compositions utilizingirreversible adhesives or compositions that irreversibly attack andbreak down the microencapsulating side wall of the encapsulated speciescontaining a color former.

Graphics and Messaging:

Messages, symbols, illustrations, titles, graphics, text, text messages,messages in general, images, icons, licensed figures, numerical values,hidden messages, line art, detailed art, multi-colored images, embeddedgraphics, graphic elements or entire graphics, visual que's, obscuredimages, partial images, pricing information, security information,promotional information, safety information, marks, patterns, and thelike can be combined with time and time-temperature color developmentprocesses and compositions described above.

Graphic and messaging information can be printed with stationary inksabove or below the time and time-temperature development compositions.Graphic and messaging information can be printed with time andtime-temperature inks and combined with stationary graphics andmessages. Likewise, both stationary and time-temperature inks can becombined in unique ways to generate messages that appear and disappear.

Graphic overlay patterns can be employed whereby the graphic overlayobscures a color developing graphic or message comprised of the time ortime temperature ink composition. As the time or time temperature inkdevelops in the initial stages, it is obscured by the stationary graphicoverlay pattern until development proceeds to an intensity that thedeveloping ink becomes discernable through the graphic overlay pattern.

Alternatively, a developing graphic or image comprising the developingink can be printed in a trapped pattern that is compatible or continuouswith the developing ink. Initially, the message is apparent. As thedeveloping ink continues to develop, it will become similar in pattern,hue, and intensity with the stationary graphic. At a pre-described timeor time-temperature profile, the developing pattern color and patternmatches the stationary pattern and becomes indiscernible against thebackground and the message or graphic appears to disappear.

A wide range of graphic and messaging formats can be utilized toemphasize, obscure, confuse, re-register, change, morph, transition,alter, become apparent, alter, integrate or the like to achieve adesired result that best suit the readout or resulting effect intendedfor a particular product application of interest. Examples stated aboveare cited by way of emphasizing a wide range of options, but notintended as limitations.

Conversion of AFM to High-Resolution Thermal Printing System UsingPrinted Dye Systems:

AFM with a heater tip can be utilized for high resolution colordevelopment based upon differentiated RGB color change pigments. Fullcolor image development based on high resolution marking throughselective identification of pigment particles even though particles arerandomly printed.

Integration of Visual Time and Time-temperature Compositions andConstructs into Microelectronic Recording Devices:

Microelectronic time and time-temperature devices capable of recordinghistorical and/or real time histories of temperatures over time benefitfrom integration of visual time and time-temperature indicating systemsdescribed herein by providing in addition to electronic readouts, visualindications directly on the recording device or label.

By way of example, but not limitation, time and/or temperatureindicating regions can be integrated with micro-electronic heatingelements and/or flash imaging circuits that are powered and tripped bythe microelectronic device during a time or time-temperature recordingsession. The heating element can be used to develop a localizedtemperature high enough to irreversibly trigger a color change in thejuxtaposed irreversible thermochromic layer.

The combination of a microelectronic digital historical data set and avisual color change element provides users of the device with a noveloption of visualizing immediately whether a temperature threshold hadbeen breached along with a historic data recording of the time andtemperature history of a product that the integrated device had beenattached to.

Reversal of Pre-Colored/Triggered Compositions as Time and TimeTemperature Indicating Compositions and Articles:

Pre-colored/triggered color former and color developer compositions canbe printed on amenable substrates including papers, films, and otherconvenient mediums for product formats. Pre-colored donor/acceptorcomplexes can be dissociated using mild basic mediums. Mild basicmediums can be delivered to the pre-colored/triggered complexes by avariety of means including adhesive compositions comprising a basiccomposition that can intimately interact over time and/or temperatureparameters to change the colored complex to a non-colored medium.

Alternatively and by way of example, but not limitation, a basic inkcomposition can be marked or printed onto the pre-colored composition todeliver a metered amount of neutralizing medium and thus reverse thecolor to a colorless state. The color decay process can be correlatedover time and time temperature to generate indicating devices that canserve as alternative time indicating sensors, time-temperature sensors,and temperature monitoring sensors. Methods described herein forblocking, acceleration, product embodiments, processes and the like forcolor generating process can be readily utilized as practical means toenable the color decay process

A wide range of commercially available marking inks includingfluorescent inks, resins, dyes, liquid concentrates, marking pens,fluorescent markers, basic glues, glue sticks, emollients, gels, basicadhesive tapes, basic pressure sensitive labels, pressure sensitiveadhesive compositions, ink-jet inks, and a variety of related oralternative mediums for delivering a metered amount of basic medium tostimulate color reversal for a time or time temperature dependentindicating process can be employed.

Color generated color forming/color developing compositions can bepre-colored using various stimuli including co-solvation, aggressivemixing, frictional mixing, co-melting, and the like. The pre-coloredcomplex of a donor and acceptor can be readily formulated as an ink orcoating. Pre-coloration can also be process post printing throughtreatments described above. Subsequently, the color decay processesherein can be employed as a time and time temperature indicating means.

Spot Color Decaying Adhesives:

Printable spot color development adhesives were can be prepared usingcolor decaying basic compositions, tackifying compounds, and ancillarybinding agents and resins. Spot printed adhesives have the advantageover flood coated adhesive in making time and time temperatureindicating constructs in that the spot adhesive can be selectivelyprinted, pattern, and positioned in selective areas for desired andenhanced effects. Of interest are commercially available color decayingcompositions, Fluorescent makers, sun-screen stick (Banana Boat), etc.

Buffering Agents and Capacities:

A buffer solution is an aqueous solution consisting of a mixture of aweak acid and its conjugate base or a weak base and its conjugate acid.It has the property that the pH of the solution changes very little whena small amount of acid or base is added to it. Buffer solutions are usedas a means of keeping pH at a nearly constant value in a wide variety ofchemical applications.

A wide range of buffering solutions can be employed to assist in theregulation of color forming and color decaying applications. Bufferingcompositions can include, but are not limited to: phosphate buffering,PBS, tris-buffers, and like. Useful buffer mixtures are listed below:

pH Components range HCl, Sodium citrate 1-5 Citric acid, Sodium citrate2.5-5.6 Acetic acid, Sodium acetate 3.7-5.6 Na₂HPO₄, NaH₂PO₄ 6-9 Borax,Sodium hydroxide 9.2-11 “Universal” buffer mixtures are summarized below. By combiningsubstances with pK_(a) values differing by only two or less andadjusting the pH a wide-range of buffers can be obtained. Citric acid isa useful component of a buffer mixture because it has three pK_(a)values, separated by less than two. The buffer range can be extended byadding other buffering agents. The following two-component mixtures havea buffer range of pH 3 to 8.

0.2M Na₂HPO₄/mL 0.1M Citric Acid/mL pH . . . 20.55 79.45 3.0 38.55 61.454.0 51.50 48.50 5.0 63.15 36.85 6.0 82.35 17.65 7.0 97.25 2.75 8.0

A buffering agent adjusts the pH of a solution. The function of abuffering agent is to drive an acidic or basic solution to a certain pHstate and prevent a change in this pH. Buffering agents have variableproperties—some are more soluble than others; some are acidic whileothers are basic. As pH managers, they are important in many chemicalapplications, including agriculture, food processing, medicine andphotography.

Temperature Dependent pKa Compositions for Regulation:

An acid dissociation constant, K_(a), (also known as acidity constant,or acid-ionization constant) is a quantitative measure of the strengthof an acid in solution. It is the equilibrium constant for a chemicalreaction known as dissociation in the context of acid-base reactions.

HA=A ³¹+H⁺

where HA is a generic acid which dissociates by splitting into A⁻, knownas the conjugate base of the acid, and the hydrogen ion or proton, H⁺,which, in the case of aqueous solutions, exists as a solvated hydroniumion. In the example shown in the figure, HA represents acetic acid, andA⁻ the acetate ion. The chemical species HA, A⁻ and H⁺ are said to be inequilibrium when their concentrations do not change with the passing oftime.

EXPERIMENTAL I. Color Former/Color Developer Compositions

A. Reversible color development hydrochromic inks:

A pre-colored reversible hydrochromic ink is prepared using a twocomponent solution mixture containing developer and color former. Thedeveloper solution is prepared using 10% by weight developer (Pergafast201, Ciba AG CH) dissolved in 90% polyethylene glycol average molecularweight 1,450 g/mol (Sigma Chemicals). The mixture is brought above 200°F. and mixed until the solution becomes clear. A color former solutionis prepared using 20% by weight color developer Specialty Magent 20(Emerald Hilton Davis, LLC) dissolved in 80% by weight polyethyleneglycol average molecular weight 1,450 g/mol (Sigma Chemicals). Themixture is brought above 200° F. and mixed until the solution becomesclear. The developer solution and color former solutions are kept heatedmixed. A slight magenta color develops. The solution is allowed to coolto 160° F. 3 volumes of hot water (greater than 160° F.) is added duringvigorous mixing. An immediate magenta colored emulsion is formed and thesolution is allowed to thicken during cooling to room temperature. Theconcentrated slurry may be removed for addition to an ink vehicle orused directly as a coating ink.

B. Reversible color development hydrochromic papers:

An aqueous slurry ink is coated on standard white bond paper. Thecoating is warm air dried. The initially colored—hydrated ink isconverted to a colorless state during drying. Drying and conversion to acolorless state may be facilitated using forced warm air.

Color markings, drawings, graphics, message writing, symbols and thelike may be generated by applying a water marker, pen, swab, stamp tothe colorless coated area of the paper. Colors generated by contact withwater are observed to dissipate within minutes upon drying. The colordevelopment and color dissipation is reversible over a large number ofapplications.

C. Reversible color development composition based on ascendingtemperature:

A simplified and intense ascending reversible color development coatingcomposition is prepared using a novel single component phase separatingcolor developer and a single component color former. 83% by weight of anascending color developer glycerol monostearate (2,3-dihydroxypropylC18, GMS) is heated to 180° F. to ensure complete melting and lowviscosity. 17% by weight green color former (Pergascript™ green I-2GN,Ciba AG CH) is added as a powder, mixed and heated (>180° F.) untilcompletely dissolved. The color former is observed to turn deep green asit dissolves to a rich dark green mixture. The mixture retains a deepgreen color provided that it remains molten. Cooling to room temperatureresults in a transition of the formulation to an off-white slightlytinted waxy solid.

D. Reversible ascending temperature color development substrates:

A reversible ascending temperature color change substrate is preparedusing the reversible color development composition prepared in ExampleC. A solidified room temperature composition is heated to 160° F. untilit is deep green and molten. The molten composition is then applied topaper substrates by a variety of standard coating processes. Forconvenience, the composition is roller coated on a standard 80 poundbonded white paper. Rollers are pre-warmed to ensure even coating.Uniform coatings are applied to paper substrates. The coatings coolrapidly at room temperature (68° F.). Initially colored coatings turnfrom a deep green coloration to a translucent off white color uponcooling. The coating penetrates well into the paper substrate providinggood stability on the paper. Cooled non-colored coatings are changedfrom colorless state to a colored state upon raising the temperatureabove the melting transition of the ascending color developer glycerolmonostearate. The color completely reverses upon cooling back to roomtemperature. The ascending color change is reversible over continuedrepeated cycles and long term storage.

E. Micro-encapsulation of reversible color development compositions baseon ascending temperature:

An ascending reversible color development coating composition isprepared using a novel single component phase separating color developerand a single component color former is prepared in accordance to ExampleC above. 83% by weight of an ascending color developer glycerolmonostearate (2,3-dihydroxypropyl C18, GMS) is heated to 180° F. toensure complete melting and low viscosity. 17% by weight green colorformer (Pergascript™ green I-2GN, Ciba AG CH) is added as a powder,mixed and heated (>180° F.) until completely dissolved. The colordeveloper turns deep green as it dissolves to a rich dark green mixture.The mixture retains a deep green color provided that it remains molten.The mixture is homogenized and dispersed in an aqueous medium until theaverage particle size is 2 microns. The color former dispersion is thenadmixed by stirring first with a 70% strength by weight aqueous solutionof melamine-formaldehyde resin (molar ratio of melamine:formaldehyde1:6) and a 20% strength by weight aqueous solution ofpolyacrylamidomethylene-propanesulfonic acid in a weight ratio of 1:1and subsequently with a normalizing amount of sodiumdihydrogenphosphate. The mixture is then adjusted with formic acid to pH4.2. After mixing at room temperature for one hour and the addition of2.5 g of water, the mixture is stirred at 160° F. for 2 hours untilcuring was complete.

A micro-encapsulated slurry is obtained in approximately 30-40% byweight aqueous dispersion of ascending reversible color generatingreverse leuco dye which is colorless at room temperature and becomesreversibly intensely colored above the melting transition of theco-developer/solvent GMS.

The micro-encapsulated composition subsequently is either separated anddried to a powder form to be admixed to non-aqueous printing vehiclessuch as UV curable ink resins or solvent based in resins or is useddirectly as an additive to aqueous slurry to be added to aqueous basedprinting vehicles.

F. Separate reversible red, blue, and green (RGB) color developmentcompositions based on ascending temperature for color image development:

Color enriched ascending reversible color development coatingcompositions are prepared using a novel single component phaseseparating color developer and a single component color formers. 80% byweight of an ascending color developer glycerol monostearate(2,3-dihydroxypropyl C18, GMS) is heated to 180° F. to ensure completemelting and low viscosity. 20% by weight either red, blue, or greencolor formers (Pergascript™, Ciba AG CH) are added as powders, mixed andheated (>180° F.) until completely dissolved. The color formers turndeep independent colors as they each dissolve. The mixtures retain adeep red, blue or green color provided that they remain molten. Coolingto room temperature results in a transition of the formulation to anoff-white slightly tinted waxy solid.

Each RGB color development composition is utilized in a 3-color printingprocess to generate a realistic color image. The initial printingprocesses require careful plate positioning to ensure colorregistration. Color printing is accomplished while the color developmentcompositions are elevated in temperature and in the colored state. Uponcooling to room temperature, the image disappears on the paper printingsubstrate. As the substrate is warmed, the image appears from a blankpage reversibly until the page is cooled again back to room temperature.The reversible ascending temperature effect provides an unusual anunexpected image development process as compared to standard availableleuco dye compositions that can only be used to reveal an underlyingimage.

G. Separate reversible red, blue, and green (RGB) color developmentcompositions and generation of hydrochromic full color imagedevelopment:

Color enriched hydrochromic reversible color development coatingcompositions are prepared using novel color former/developercompositions. Pre-colored RGB reversible hydrochromic inks are preparedusing independent two component solution mixtures containing developerand color former as described in Example I. The developer solutions areprepared using 10% by weight developer (Pergafast 201, Ciba AG CH)dissolved in 90% polyethylene glycol average molecular weight 1,450g/mol (Sigma Chemicals). Each mixture is brought above 200° F. and mixeduntil the solution becomes clear.

Separate color former solutions are prepared using 20% by weight colordeveloper Specialty Red, Specialty Blue, or Green (Emerald Hilton Davis,LLC) dissolved in 80% by weight polyethylene glycol average molecularweight 1,450 g/mol (Sigma Chemicals). The mixture is brought above 200°F. and mixed until the solution becomes clear.

Corresponding color developer solutions and color former solutions arekept heated mixed and kept independent. Slight colors are developed uponmixing. The solutions are allowed to cool to 160° F. 3 volumes of hotwater (greater than 160° F.) are added during vigorous mixing. Animmediate red, blue or green colored emulsion is formed and thesolutions are allowed to thicken during cooling to room temperature. Theconcentrated slurries can be removed for addition to an ink vehicle orused directly as a coating ink.

The aqueous slurry inks are printed in RGB patterns on standard whitebond paper. The coating is warm air dried. The initiallycolored—hydrated ink is converted to a colorless state during drying.Drying and conversion to a colorless state are facilitated using forcedwarm air.

Full color images, multi-colored markings, drawings, graphics, messageswriting, symbols and the like can be generated by applying a watermarker, pen, swab, or stamp to the colorless coated area of the paper.Colors generated by contact with water are observed to dissipate withinminutes upon drying. Color image development and color dissipation arereversible over a large number of applications.

H. Coacervation micro-encapsulation of reversible color developmentcompositions for ascending temperature color change dyes:

150 ml 8% aqueous solution of 200 Bloom Type A Gelatin at 50° C. iscombined together with 0.1 ml of n-octanol as a foam suppressant. 80 gmof 2,3-glycerol monostearate is pre-mixed with 20 gram color formerPergascript™ orange I-G (Ciba AG CH) and then mixed into the aqueoussolution with agitation to form oil phase droplets in the range of 10-20microns. The emulsion pH is adjusted to pH 5. 10 ml of a 28% solution ofsodium polyaspartate diluted with an additional 40 ml of water is addedto the emulsion during mixing. An additional 170 ml of distilled wateris subsequently added. The pH of the mixture is then lowered to 4.4 byaddition of glacial acetic acid. The mixture is cooled to about 10° C.and the pH lowered to pH 4.2. The solution is allowed to cool 45 minutesat 10° C. whereby 5 ml of a 25% glutaraldehyde solution is added and themixture allowed to stay 12 hour at 22° C.

The micro-encapsulated composition is subsequently either separated anddried to a powder form to be admixed to non-aqueous printing vehiclessuch as UV curable ink resins or solvent based in resins or is useddirectly as an additive to aqueous slurry to be added to aqueous basedprinting vehicles.

I. Natural co-developer-solvent based leuco dye compositions:

A natural co-developer-solvent leuco dye is prepared by pre-melting 80%carnauba wax to 100° C. Color former is added at 20% by weight andmixed. The mixture is heated and mixed until the color developer iscompletely dissolved into a clear molten solution. The molten solutionis allowed to cool to room temperature. Upon cooling the composition issolidified to a rich deep color. The solidified colored compositionexhibited fully reversible color change characteristics upon heating andmelting and chilling and solidification. The solidified compositioncould be used directly as a coating or converted to a powdered form foraddition to printing vehicles, plastics extrusion compositions,injection molding compositions or the like.

J. Aqueous coating and product additive slurries using naturalco-developer-solvent based leuco dye compositions:

Aqueous slurries of natural co-developer-solvent based leuco dyecompositions prepared as described in Example I above are emulsifiedusing food-grade surfactants and ultra-sonication. A 20% by weightemulsifier solution of Protanal Ester BV 3750 (FMC Biopolymer) isprepared by adding and mixing the surfactant in stirring water at 70° C.until the emulsifier is completely dissolved. 50% by weight naturalco-developer-solvent based leuco dye compositions are heated to aliquefied state (100° C.). 50% by weight pre-heated emulsifier solutionis added and the mixture is sonicated using a 300 watt ultrasonicatorprobe. A uniform slurry emulsion is formed within 2 minutes ofsonication. The slurry is allowed to cool to room temperature. Theslurry may be used directly as a coating ink or utilized at variousconcentrations as an additive to ink vehicles. Pre-formed slurries canbe further micro-encapsulated using standardized micro-encapsulationprocesses describe above.

K. Leuco dye/polydiacetylenic combinatorial compositions in whichdiacetylenic moieties serve as color developers and possess intrinsiccolor change polymer characteristics:

10% by weight color formers—either red, blue, or green (Pergascript™,Ciba AG CH) and 10% by weight 10,12-tricosadiynoic acid (C23) aredissolved is dichloromethane. The presence of the free monomeric C23acid initiates color development in solution. The solutions are tintedrelative to the color type. Each formulation is dried on to paper. Theresulting colors are rich in hue. Each color type exhibits a reversiblecolor change when elevated above 160° F. Dried color draw-downs aresubsequently exposed to UV light (254 nm) resulting in the formation ofan additional blue hue to each color type exposed. The blue hue sgenerated by the topochemical polymerization reaction forming theene-yne polydiacetylenic polymer backbone. The blue hue may beirreversibly changed to a red hue during heating or through frictionallyinduced mechanochromic triggering. The leuco dye reversible color changeis convoluted with the polydiacetylenic color transition.

L. Solvent based compositions for inkjet, drop-on-demand, and continuousinkjet printing:

10-15% by weight color formers and developers are dissolved in solventsystems including ratios of chloroform, methylethyl ketone, and alcoholtypes. Soluble resins such as polyethylene glycol and other soluble, butadherent polymers may be used. Soluble solutions are used directly asprinting ink compositions in various inkjet, drop-on-demand, andcontinuous inkjet printing formats.

M. Developers comprising one adhesive layer can be adhered to standardthermal printing paper to develop a time dependent image:

Developers comprising adhesives used in tapes and pressure sensitivelabels are contacted with commercially available and standard thermalprinting used for printing paper receipts at checkout. Color isdeveloped in the thermal printer based on the developer migrating fromthe adhesive layer to the color former layer in the thermal paper.Further, the adhesive may be selectively patterned to generate imagesthat develop as time progresses after contacting the patterned adhesivelayer with the color development layer.

N. A developer comprising one component of a printed layer and a colordeveloper comprising a second component is color/time activated using aslow migrating adhesive/solvent:

A micro-encapsulated developer and color former are co-printed such thatno color is developed after printing had been accomplished. The slowmigrating solvent effect of an adhesive layer acts to dissolve theencapsulation layer from the developer thereby releasing the developerto initiate a color change in the color former. Further adhesive may beselectively patterned to generate images that develop as time progressesafter contacting the patterned adhesive layer with the color developmentlayer.

O. Compositions of the invention find use in a variety of differentapplications, including but not limited to:

-   -   Novel color development for cold chain management:    -   Ascending temperature indicator as color is develops    -   Ascending temperature indicator where color development lock        occurs at set points:    -   Shunted color development dependent on time along one axis and        temperature along another:    -   Site addressable flash imaging using ascending temperature leuco        dyes:    -   3D flash imaging using ascending temperature leuco dye:    -   Message that appears as color develops rather than ink opacity        changing to make message appear:    -   Reversible color development candles:    -   Reversible color development printable dyes:    -   Irreversible color development thermal inks and papers:    -   Toys applications that turn color upon touching:    -   Ascending temperature indicating composition for lotions and        emollients:    -   Physiologic temperature status determination devices:    -   Hydration indicating composition for lotions and emollients to        determine physiologic hydrations status:    -   Developers that co-act as alternative active agents e.g.        flavors, fragrances, stimulants:    -   Long-term hysteresis effect and reversal using water        reactivation based on aqueous slurry inks:    -   Long-term hysteresis effect and reversal using heat reactivation        based on aqueous slurry inks:    -   Novel flexographic in-line layering/manufacturing as a        production means for tunable color indicating systems:    -   Ultra sharp critical melting point mediums for digital color        development:    -   Ascending reversible color development leuco dye    -   Ascending reversible color development leuco dye with hysteresis    -   Temperature adjustable ascending color development leuco dye    -   Micro-encapsulated ascending color development leuco dye    -   Co-solvent-developer single component molecule    -   Hydrochromic reversible color development leuco dye    -   Mixed ascending and descending reversible leuco dyes    -   Natural co-developer-solvent for ascending color development    -   Natural co-developer-solvent for descending color development    -   Single component as dual solvent and color developer properties    -   Slurry concentrates of natural ascending and descending leuco        dyes    -   Leuco dye color formers—developed by polydiacetylenic developers    -   Reversible color to colorless based on temperature    -   Reversible colorless to color based on temperature    -   Reversible color to colorless based on hydration    -   Reversible colorless to color based on hydration    -   Reversible color to colorless based on solvation    -   Reversible colorless to color based on solvation    -   Irreversible colorless to color based on temperature    -   Irreversible color to colorless based on solvation    -   Reversible non-hysteresis color change    -   Reversible color change with hysteresis types    -   Irreversible non-hysteresis color change    -   Irreversible color change with hysteresis types

II. Time and Time-Temperature Examples

A. Color referenced time and time temperature sensors using pre-mixedcolor forming compositions and activating adhesives:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives. 60° C., 75° C., 90° C. and 100° C. irreversible thermochromicink compositions (Kromagen and/or Kromax concentrate, ThermographicMeasurement Co.) are flexographically printed using a 20 anilox rolleron various paper and film stocks (pressure sensitive and non-pressuresensitive stock types). Magenta, orange, cyan, blue, turquoise, green,black and red color types are printed.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Temperatureindicating devices are prepared by applying single sided strips of Tesa4965 8.0 mil thickness adhesive strips. Upon heating above or near theirreversible ink below its normal temperature transition point, therapid onset of color development occurs.

Time indicating strips are prepared by applying single sided strips ofTesa 4965 8.0 mil thickness. Adhered adhesive color developer/colorformer constructs are left at room temperature for 14 days. Colordevelopment is monitored over time and compared to a stationaryreference color and correlated with time during the color developmentprocess.

B Low temperature time-temperature indicating devices using pre-mixedcolor forming compositions and activating adhesives:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives above.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Temperatureindicating devices are prepared by laminating, but separated withremovable pull tab single sided strips of Tesa 4965 8.0 mil thickness.

Upon applying a time-temperature indicating device to a cold foodproduct and allowing for quick cooling of the indicating device, thedevice is activated by removing the pull tab. Color development remainsdormant at refrigerator temperatures (40-45° F.) for several days. Uponremoving the adhered activated device from refrigerator temperatures toroom temperature, color development begins occurring within the first1-3 hours of elevated temperature exposure (72° F.). Color developmentcontinues with continued elevated exposure and at each time durationmatched a pre-determined reference color calibrated to a given exposuretime.

C. Obscured graphic time and time temperature sensors using pre-mixedcolor forming compositions and activating adhesives:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives as above. Visible obscuring graphics are generated incombination with pattern printed sensitive ink patterns.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Temperatureindicating devices are prepared by applying single sided strips of Tesa4965 8.0 mil thickness adhesive strips. Upon heating above or near theirreversible ink below its normal temperature transition point, therapid onset of color development occurs.

Time indicating strips are prepared by applying single sided strips ofTesa 4965 8.0 mil thickness. Adhered adhesive color developer/colorformer constructs are left at room temperature for 14 days. Colordevelopment is monitored over time and compared to a stationaryreference color and correlated with time during the color developmentprocess. Graphics and colorations are designed and printed to optimizethe appearance of an image through the overlay patterns. The resultingimage development process improves the end-point appearance of atemperature and/or time delay pattern.

D. Time and time temperature sensors using long chain alcohols andactivating adhesives:

Long chain alcohols can be used to regulate, mitigate, slow, andmodulate color development in a time and temperature dependent way.Specifically, and especially utilizing an adhesive activating means inconjunction, long chain alcohols have the advantage of acting as apassive carrier for color formers, but have a highly mitigating effecton causing color development. Their transition melting temperatures canaccommodate a wide range of time and time temperature applications.

A mixture containing 0.5 gm Magenta 20 (Hilton Davis, LLC) and 2.5 gmUnilin 700 series (Baker Hughes Inc.) is heated above the co-mixedmelting transitions (greater than 100° C.) until both components arecompletely solubilized. The transparent solution is thoroughly mixed anddirectly coated on substrates from the melt. Further melting isaccomplished after coats are applied to improve uniformity andadsorption into substrates.

Temperature indicating devices are prepared by applying single sidedstrips of Tesa 4965 8.0 mil thickness adhesive strips. Upon heatingabove or near the melting transition of the Unilin 700 series alcohol,the rapid onset of magenta color development occurs.

Time indicating strips are prepared by applying single sided strips ofTesa 4965 8.0 mil thickness. Adhered adhesive color developer/colorformer constructs are left at room temperature for 14 days. Colordevelopment is monitored over time and compared to a stationaryreference color and correlated with time during the color developmentprocess.

E. Reversible/Irreversible ascending temperature monitoring:

Magenta 20 is mixed at 10% by weight with glycerol monostearate (GMS),heated, and dissolved. The heating process leads to a color developmentin the melt as GMS acts both as a solvent to the color former as well asa color developer. The molten mixture is printed on paper and filmsubstrates. Upon cooling the intense color reverses to a cleartransparent state as the GMS solidifies. Color development is reversiblewith hot and cold temperature cycling above and below the meltingtransition of GMS.

Temperature indicating devices are prepared by applying single sidedstrips of Tesa 4965 8.0 mil thickness. Upon heating above or near themelting transition of GMS, the rapid onset of magenta color developmentoccurs. Color development becomes irreversible in the presence ofadhesive coated regions. In contrast, color development is reversible inareas on non-adhesive coated regions.

Multi ascending reversible and irreversible temperature indicating andirreversible time indicating devices may be prepared for monitoringvarious medium to high temperature process and control steps. Printedareas become an ascending reversible thermochromic layer as well as anirreversible heat sensitive time temperature ink in the presence of anadhesive activating layer for a plurality of optical sensingcapabilities.

F High temperature—time indicating constructs:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives. 60° C., 75° C., 90° C. and 100° C. irreversible thermochromicink compositions (Kromagen and/or Kromax concentrate, ThermographicMeasurement Co.) are flexographically printed using a 20 anilox rolleron various paper and film stocks (pressure sensitive and non-pressuresensitive stock types). Magenta, orange, cyan, blue, turquoise, green,black and red color types are printed.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Temperatureindicating devices are prepared by applying single sided strips of Tesa4965 8.0 mil thickness alone or in combination with a blocking layeradhesive (Arlon 301 transfer adhesive 2.0 mil thickness). Upon heatingabove or near the irreversible ink below its normal temperaturetransition point, the rapid onset of color development occurs withoutthe blocking or delay layer (160° F. for 10-60 minutes). Delayed colordevelopment occurs using the block or delay layer (160° F., 1-3 hours).

G. Hydrocarbon blocking and delay layers:

Blocking and delay layers are produced with micro-crystalline waxes,paraffins, and pure hydrocarbon layers and coatings. Pre-mixed colorforming compositions and inks are utilized as time and time temperatureindicating systems in combination with activating adhesives printed asabove. Hydrocarbon compositions are post coated in fractional milthicknesses directly onto the pre-mixed mixed color forming compositionsand inks.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Temperatureindicating devices are prepare by applying single sided strips of Tesa4965 8.0 mil thickness alone or in combination with a blocking layeradhesive (Arlon 301 transfer adhesive 2.0 mil thickness). Upon heatingabove or near the irreversible ink below its normal temperaturetransition point, the rapid onset of color development occurs withoutthe blocking or delay layer (160° F. for 10-60 minutes). Delayed colordevelopment occurs using the block or delay layer (160° F., 1-3 hours).

H. Color referenced time security badge an 24 your promotional labelusing pre-mixed color forming compositions and activating adhesives:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives. 60° C., 75° C., 90° C. and 100° C. irreversible thermochromicink compositions (Kromagen and/or Kromax concentrate, ThermographicMeasurement Co.) are flexographically printed using a 20 anilox rolleron various paper and film stocks (pressure sensitive and non-pressuresensitive stock types). Magenta, orange, cyan, blue, turquoise, green,black and red color types are printed.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Time indicatingsecurity badges and promotional labels are prepared as by applyingsingle sided strips of Tesa 4965 8.0 mil thickness. Adhered adhesivecolor developer/color former constructs are left at room temperature for0-24 hours. Color development is monitored over time and compared to astationary reference color and correlated with time during the colordevelopment process.

I. Time indicating graphic comprising a thermally printed securitylabel: Pre-mixed color forming compositions and inks are utilized astime and time temperature indicating systems in combination withactivating adhesives. 60° C., 75° C., 90° C. and 100° C. irreversiblethermochromic ink compositions (Kromagen and/or Kromax concentrate,Thermographic Measurement Co.) are flexographically printed using a 20anilox roller on various paper and film stocks (pressure sensitive andnon-pressure sensitive stock types). Magenta, orange, cyan, blue,turquoise, green, black and red color types are printed on pressuredirect thermal label stock as an adjunct security badge.

The security badge can be directly thermally printed with visitor, date,time, and intended information using a digital thermal printer, printdriver, and operating software. Printed graphics are designed such thatthe direct thermal print information is printed in regions other thanwhere the time-dependent color former ink composition is printed.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Temperatureindicating devices are prepare by applying single sided strips of Tesa4965 8.0 mil thickness. Upon heating above or near the irreversible inkbelow its normal temperature transition point, the rapid onset of colordevelopment occurs.

Time indicating strips are prepared by applying single sided strips ofTesa 4965 8.0 mil thickness to regions where the color forming ink isprinted adjacent to where direct thermal print mater is printed usingthe thermal printer. Adhered adhesive color developer/color formerconstructs are monitored periodically for time-based securityapplications at room temperature from 1-48 hours. Color development ismonitored over time and compared to a stationary reference color andcorrelated with time during the color development process.

J. Direct thermal paper conversion to time indicating devices:

Commercially available direct thermal coated substrates are convertedinto a time only indicating substrate depending upon the thermal coatingcomposition and provided protective coating. An aggressive adhesiveoverlay containing a solvent and acidic polymeric adhesive is applied atroom temperature to the direct thermal label. The thermal label issourced from thermal label supplier and printed with various overlaygraphics. The thermal label type is minimally coated with a protectivelayer so that the onset of color development in the direct thermalcoating can be activated with the adhesive overlay.

Color development is monitored at room temperature and daily over timeto observe color development. After 1 day a light gray begins to appear.Daily, the color begins to gradually develop until the gray begins tobecome more saturated. The gray color development process is compared toa gray scale. The gray scale is calibrated graphically so that the colordevelopment process can be matched and compared against an ascendingdaily schedule. Various short and long time frame duration indicatorsare developed for a variety of time scales and product timingapplications.

K. Direct thermal paper conversion to short duration time-temperatureindicating label:

Commercially available direct thermal coated substrates are convertedinto a time only indicating substrate depending upon the thermal coatingcomposition and provided protective coating. An aggressive adhesiveoverlay containing a solvent and acidic polymeric adhesive is applied atroom temperature to the direct thermal label. The thermal label issourced from thermal label supplier and printed with various overlaygraphics. The thermal label type is minimally coated with a protectivelayer so that the onset of color development in the direct thermalcoating may be activated with the adhesive overlay in combination withmoderately high temperatures.

Color development is monitored at 160° F. over time to observe colordevelopment. After 15 minutes the color begins to become lightly gray.Hourly, the color begins to deepen until the gray begins to become moresaturated. The gray color development process is compared to a grayscale. The gray scale is calibrated graphically so that the colordevelopment process can be matched and compared against an ascendinghourly schedule. Various short and long time frame duration indicatorsare developed for a variety of time scales and product timingapplications. Different time and temperature profiles are developeddepending on the commercially available thermal label stock and theaggressive nature of the color developing adhesive layer comprising theactivating laminate.

L. Aqueous PAA solution co-mixed with microcrystalline color former:

Polyacrylic acids including molecular weight cutoffs from 800 grams/molto 10,000,000 grams/mole are formulated as color developing carrierresins with micro-particulate color forming agents. Aqueous suspensionsor dispersions are made with individual molecular weight type of PAA's.PAA's are dissolved or suspended at between 1-10% by weight in water.Solution pH may be adjusted accordingly to increase or decrease acidity.

Milled or ground suspension of micro-crystalline color formers Magenta20, green, orange, red, yellow or (Hilton Davis, LLC), crystal violet(Sigma Aldrich Co.), or orange, magenta, red, black, blue, or green(Ciba Corp), are admixed with the aqueous solutions of each PAA. Aftercomplete mixing or emulsification, the ink-like solutions can be printeddirectly on to paper or film substrates. Profiles for temperature andtime temperature readings are recorded.

M. Promotional time-color development using metallochromic effect:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives. 60° C., 75° C., 90° C. and 100° C. irreversible thermochromicink compositions (Kromagen and/or Kromax concentrate, ThermographicMeasurement Co.) are further formulated with high luster aluminumpowders/pastes to provide a metallic luster. Aluminum powders/pastes areadded at between 2-15% by weight depending on the metallic lusterdesired. Samples are printed using a 20 anilox hand roller on variouspaper and film stocks (pressure sensitive and non-pressure sensitivestock types). Magenta, orange, cyan, blue, turquoise, green, black andred color types are formulated and printed.

Labels are die-cut in-line. Reference color graphics are simultaneouslyprinted in-line using color hues and intensities calibrated as referencecolors for given temperature and time applications. Temperatureindicating devices are prepared by applying single sided strips of Tesa4965 8.0 mil thickness. Upon heating above or near the irreversible inkbelow its normal temperature transition point, the rapid onset of colordevelopment occurs

Time indicating strips prepared are by applying single sided strips ofTesa 4965 8.0 mil thickness. Adhered adhesive color developer/colorformer constructs are left at room temperature for up to 7 days. Initialprinted samples give a rich silver metallic luster. Color development ismonitored over time and compared to a stationary reference color andcorrelated with time during the color development process. Final colorsare brilliant mixtures of metallic luster and color former typesselected.

N. Full color image development:

Three color graphics are produced of images at 200 DPI and colorseparation is performed. Color separated flexographic plates areproduced using standard processes. Pre-mixed color forming ink basesincluding red, blue, and green are printed in a three color flexographicprinting process in the undeveloped state using a Mark Andy flexographicprinting press.

Images are die-cut in-line. Temperature indicating images are preparedby applying single sided strips of Tesa 4965 8.0 mil thickness. Uponheating above or near the irreversible ink below its normal temperaturetransition point, the rapid onset of color development occurs. Timeindicating images are prepared by applying single sided strips of Tesa4965 8.0 mil thickness. Adhered adhesive color developer/color formerconstructs are left at room temperature for up to 7 days.

N. Holographic overlays for special optical effects:

Holographic and optical overlays are utilized in conjunction with imageand pattern development using time and time temperature compositions.Translucent holographic overlay graphics and Fresnel lenses and prismsare superimposed with printed patterns of the color forming layer. Theoptical overlay can be adhered to one side or a double-stick adhesivecolor development layer such that the laminated structure is transparentand yet can be aligned with a printed color forming layer for thelaminate to be adhered to. The superposition of optical overlays and theprinted color forming printed graphic provide for unique and specializedoptical effects. For example, time and time temperature dependent imagescan be developed to provide motion or 3-D effects during the colordevelopment process.

O. Time-temperature indicating thermometer:

An ascending irreversible color indicating thermometer is made usingtime and time temperature compositions. The thermometer is designed toinitiate a color development process at temperature exposures to orabove 165° F. for greater than 5 seconds. The thermometer comprises anactivating adhesive layer, a thermal blocking layer, and a commerciallyavailable direct thermal label stock. The layered construct isassembled, die-cut, and adhered to a flat plastic pointed probe 0.25inch wide and 4 inches in length. The plastic probe is pointed on oneend for easy insertion into heated products such as foods, meats,poultry, and the like.

P. Color disappearing time indication composition and construct:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives. 60° C., 75° C., 90° C. and 100° C. irreversible thermochromicink compositions (Kromagen and/or Kromax concentrate, ThermographicMeasurement Co.) are flexographically printed using a 6 anilox roller onvarious paper and film stocks (Mark Andy printing press, pressuresensitive and non-pressure sensitive stock types).

Magenta, orange, cyan, blue, turquoise, green, black and red color typesare printed. Labels are die-cut in-line. Beginning reference colorgraphics are simultaneously printed in-line using color hues andintensities calibrated as reference colors for given temperature andtime applications. Color forming/developing inks are exposed to elevatedtemperature to develop the respective colors, patterns and images.Bright vivid colors develop above the threshold temperature of theirreversible inks. Colors are maintained and stable at room temperaturefor prolonged storage periods.

Color decaying adhesive layers are prepared using pH base adjustedwater-based adhesives. Adhesives are coated on a clear plastic filmbacking and protected with a release layer to make pressure sensitivecolor decaying adhesive strips. The color decaying adhesive strips aredie-cut and prepared as pressure sensitive labels in roll stock form.

Time indicating strips are prepared by applying single sided adhesive tothe pre-color developed/printed substrates. Adhered adhesive colordecaying constructs are left at room temperature for 24 hours. Colordevelopment is monitored over time and compared to a stationaryreference color and correlated with time during the color developmentprocess. As time progresses, the color decays relative to thepre-printed reference colors.

The extent to which color decay may be accelerated depends on thepre-coloration conditions of the pre-colored printed mediums, thechemical diffusiveness of the substrate printed on, the final pHadjusted basic conditions of the color decaying adhesive composition,mobilizing tackifying compositions used in the adhesive layer, time andtemperature and the like.

Q. Low time temperature color decaying indicating composition andconstruct:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with color decayingadhesives above. Labels are die-cut in-line. Reference color graphicsare simultaneously printed in-line using color hues and intensitiescalibrated as reference colors for given temperature and timeapplications. Temperature indicating devices are prepared by laminating,but are separated with removable pull tab single sided strips of theadhesive layer prepared as described above.

Upon applying a time-temperature indicating device to a cold foodproduct and allowing for quick cooling of the indicating device, thedevice is activated for color decay by removing the pull tab. Colordecay remains dormant at refrigerator temperatures (40-45° F.) forseveral days. Upon removing the adhered activated device fromrefrigerator temperatures to room temperature, color decay beginsoccurring within the first 1-3 hours of elevated temperature exposure(72° F.). Color development continues with continued elevated exposureand at each time duration matched a pre-determined reference colorcalibrated to a given exposure time.

R. Color dissipating marking means for time indication:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives. 60° C., 75° C., 90° C. and 100° C. irreversible thermochromicink compositions (Kromagen and/or Kromax concentrate, ThermographicMeasurement Co.) are flexographically printed using a 6 anilox roller onvarious paper and film stocks (Mark Andy printing press, pressuresensitive and non-pressure sensitive stock types).

Magenta, orange, cyan, blue, turquoise, green, black and red color typesare printed. Labels are die-cut in-line. Beginning reference colorgraphics are simultaneously printed in-line using color hues andintensities calibrated as reference colors for given temperature andtime applications.

Color forming/developing inks are exposed to elevated temperature todevelop the respective colors, patterns and images. Bright vivid colorsdevelop above the threshold temperature of the irreversible inks. Colorsare maintained and stable at room temperature for prolonged storageperiods.

Color decaying marking inks are prepared using pH base adjustedwater-based resins. Felt tip ink marking pens are filled to make colordecaying marking pens. The color decaying pens are cap sealed andprepared for use with color developed printed mediums. Ancillaryfluorescent colors additives may be used as tracer compositions and toprovide additional optical features to the color developing marks.

Time indicating strips are prepared by using the pre-colordeveloped/printed substrates. Time indicating color decaying strips aremarked and left at room temperature for marked color dissipation. Colordecay is monitored over time and compared to a stationary referencecolor and correlated with time during the color development process. Astime progresses, the color decays relative to the pre-printed referencecolors.

The extent to which color decay may be accelerated or decelerateddepends on the pre-coloration conditions of the pre-colored printedmediums, the chemical diffusiveness of the substrate printed on, thefinal pH adjusted basic conditions of the color decaying inkcomposition, and the like.

S. Plural messaging message development/message decay time indicationcomposition and construct for price tag evolution:

Pre-mixed color forming compositions and inks are utilized as time andtime temperature indicating systems in combination with activatingadhesives. 60° C., 75° C., 90° C. and 100° C. irreversible thermochromicink compositions (Kromagen and/or Kromax concentrate, ThermographicMeasurement Co.) are flexographically printed using a 6 anilox roller onvarious paper and film stocks (Mark Andy printing press, pressuresensitive and non-pressure sensitive stock types).

Magenta, orange, cyan, blue, turquoise, green, black and red color typesare printed, but printed messages, pricing information and colors arenot developed. Labels are die-cut in-line. These printed areas areregistered as areas where information would appear over time using theadhesive development layer. Beginning reference color graphics aresimultaneously printed in-line using color hues and intensitiescalibrated as reference colors for given temperature and timeapplications.

In a second location of the printed labels, printed messages, pricinginformation and colors are developed using heat as developer. Theselocations are sequestered relative to the undeveloped regions andregistered as areas where information disappears or decays over timeusing an adhesive layer formulated to dissipate the printed-activatedareas.

Labels are die-cut in-line. Color forming/developing inks are exposed toelevated temperature to develop the respective colors, patterns andimages. Bright vivid colors develop above the threshold temperature ofthe irreversible inks. Colors are maintained and stable at roomtemperature for prolonged storage periods.

Color decaying adhesive layers are prepared using pH base adjustedwater-based adhesives. Adhesives are coated on a clear plastic filmbacking and protected with a release layer to make pressure sensitivecolor decaying adhesive strips. The color decaying adhesive strips aredie-cut and prepared as pressure sensitive labels in roll stock form.

Color activating adhesive layers are prepared as spot printed adhesivesdescribe above. Both activating and decaying adhesives are coated on aclear plastic film backing and protected with a release layer to makepressure sensitive color decaying adhesive strips. Position of eachactivating and decaying adhesive types are registered according thecorresponding regions of developed or undeveloped inks representing therespective pricing information, patterns and images.

Corresponding price and message changing labels are prepared by applyingadhesives to the pre-color developed/printed substrates andnon-developed regions. Adhered adhesives demonstrate shifts in thedecaying portion of the construct over a 30 day period so that originalmessaging and pricing disappears over time. Likewise, the colorgenerating/developing adhesive layer demonstrates shifts in the messagearea showing new pricing information appearing over the same 30 dayperiod.

Pricing and messaging formats for the appearance of new information anddisappearance of original information find use in a number of pricing,promotional, advertising, inventory control, security and othercommercial, retail, industrial, service, and other fields where usersneed only apply one label or article and that label or article wouldshift in information over a desired timeframe.

The extent to which color decay can be accelerated or decayed depends onthe pre-coloration conditions of the pre-colored printed mediums, thechemical diffusiveness of the substrate printed on, the final pHadjusted basic conditions of the color decaying adhesive composition,mobilizing tackifying compositions used in the adhesive layer, time andtemperature and the like.

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity ofunderstanding, it is readily apparent to those of ordinary skill in theart in light of the teachings of this invention that certain changes andmodifications may be made thereto without departing from the spirit orscope of the appended claims.

Accordingly, the preceding merely illustrates the principles of theinvention. It will be appreciated that those skilled in the art will beable to devise various arrangements which, although not explicitlydescribed or shown herein, embody the principles of the invention andare included within its spirit and scope. Furthermore, all examples andconditional language recited herein are principally intended to aid thereader in understanding the principles of the invention and the conceptscontributed by the inventors to furthering the art, and are to beconstrued as being without limitation to such specifically recitedexamples and conditions. Moreover, all statements herein recitingprinciples, aspects, and embodiments of the invention as well asspecific examples thereof, are intended to encompass both structural andfunctional equivalents thereof. Additionally, it is intended that suchequivalents include both currently known equivalents and equivalentsdeveloped in the future, i.e., any elements developed that perform thesame function, regardless of structure. The scope of the presentinvention, therefore, is not intended to be limited to the exemplaryembodiments shown and described herein. Rather, the scope and spirit ofpresent invention is embodied by the appended claims.

1-35. (canceled)
 36. A method of preparing a color change compositionthat transitions from a first color state to a second color state uponapplication of an applied stimulus, the method comprising contacting acolor former with a color developer.
 37. The method according to claim36, wherein the method further comprises contacting the color former andcolor developer with an emulsifier and a resin.
 38. The method accordingto claim 36, wherein the method comprises preparing an aqueous slurry.39. The method according to claim 36, further comprising comprisesdrying the color change composition.
 40. The method according to claim36, further comprising preparing a powder form of the color changecomposition.
 41. The method according to claim 36, wherein the colorformer changes color in response to a phase transition of the colordeveloper.
 42. The method according to claim 36, wherein the colordeveloper comprises a glycerol monostearate derivative.
 43. The methodaccording to claim 36, wherein the color developer comprises apolydiacetylene.
 44. The method according to claim 36, wherein the colorformer comprises a thermochromic dye.
 45. The method according to claim36, wherein the color former comprises two or more distinct leuco dyes.46. The method according to claim 45, wherein the two or more distinctleuco dyes exhibit opposing color transition characteristics in responseto the same applied stimulus.
 47. The method according to claim 36,further comprising microencapsulating the color change composition. 48.The method according to claim 36, wherein the color change compositiontransitions from a colorless state to a colored state upon exposure toincreasing temperature.
 49. The method according to claim 36, whereinthe color change composition transitions from a colored state to acolorless state upon exposure to increasing temperature.
 50. The methodaccording to claim 36, wherein the color change composition transitionsfrom a colorless state to a colored state upon exposure to increasingsolvation.
 51. The method according to claim 36, wherein the compositiontransitions from a colored state to a colorless state upon exposure toincreasing solvation.
 52. The method according to claim 36, wherein thetransition is reversible.
 53. The method according to claim 36, whereinthe transition is irreversible.